CN102206717A - Method for preparing zirconium-aluminum multi-metal tanning liquor - Google Patents
Method for preparing zirconium-aluminum multi-metal tanning liquor Download PDFInfo
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Abstract
The invention discloses zirconium-aluminum multi-metal tanning liquor and a preparation method thereof. The preparation method is characterized by comprising the following steps of: dissolving 5 to 20 weight parts of zirconium sulfate and 20 to 80 weight parts of aluminum sulfate by using 0.2-0.8mol/L aqueous solution of sulfuric acid into solutions at different concentrations, mixing, and adding 0.5 to 10 weight parts of masking agent to obtain the zirconium-aluminum multi-metal tanning liquor. The multi-metal tanning liquor is applied to tanning cowhide and goat leather so as to realize chromium-free tanning and radically treat chromium pollution.
Description
Technical field
The present invention relates to the preparation method that the many metals of a kind of zirconium-aluminium cooperate owse.
Background technology
In recent years, the development of China leather industry development has become world's leather industry machining center and trade center rapidly.In tanning industry, because chromic salts is made the high-performance of leather, chrome tanning has just occupied dominant position in the tanning field always since it is used.But sexavalent chrome is toxic, uses chrome tanning agent to produce bigger harm to the ecotope and the mankind for a long time, in a large number, so the development trend of the leading tanning agent of tanning industry must be ecological tanning agent (or being called green tanning agent) from now on.
The chromium-free metal tanning agent has aluminum tanning agent, zirconium tanning agent, titanium tannage agent, iron tannage agent, rare earth (helping) tanning agent etc.This class tanning agent is plentiful, nontoxic, harmless, pollution-free at China's reserves, and the tanning performance respectively has characteristics, but uses the metal tanning agent to be difficult to satisfy different performance of leather requirements individually.It is the ion of two or more non-chromium metal that the many metals of Chrome-free cooperate tanning agent, forms the polynuclear coordination compound with flexibility by " bridge closes " effect.The many metals of Chrome-free cooperate the composite tanning agent height of tanning agent precipitation pH value than same ratio component; During the reaction of they and collagen, be not each component and collagen effect simply add with, but, show more functionality than the response capacity height of each initial component.The characteristics of tanning are that look white, consolidation, and fillibility is good, but shortcoming is hard than plate, water-absorbent is big.It is careful that aluminum tanning leather has grain, and good-extensibility, but maximum shortcoming is not water-fast washing, skin will temperings after washing, and the revolutionary cadre is dry, and the back chap is hard, and is flat thin, almost the same with rawhide.If utilize the zirconium aluminum tanning agent to come tan leather just to bring into play the advantage of the two, overcome shortcoming, can also improve fullness ratio, the consolidation performance of finished leather simultaneously, and heat-resistant stability, particularly the soft crust leather of tanning is had and select fillibility preferably.
Cooperate tanning agent precipitation pH value composite tanning agent height than same ratio component about the many metals of the existing Chrome-free of Chrome-free multi-metal complex tanning agent both at home and abroad; During the reaction of they and collagen, be not each component and collagen effect simply add with, but, show more functionality than the response capacity height of each initial component.Zirconium a lot of reports.People such as B.Madhan have synthesized a kind of aluminium-zinc tanning agent, different ligands such as phthalic acid, Citrate trianion, tartrate etc. have been studied to the tanning influence of wet leather in vain, its shrinkage temperature can reach more than 90 ℃, the physical strength of tanning and organoleptic properties are all than the good (B.Madhan of finished leather of chromium-aluminium composite tanning technology, Raghava Rao.JALCA .2001,96:343-349).Aluminium-tannic acid-silicon combination tannage has been carried out systematic research, the result shows that the specific absorption of aluminium can reach 98%, the quantity discharged of COD and TDS also obviously descends, and develops a kind of system of ecological process hides, and the color and luster of finished leather, feel are better, its shrinkage temperature can reach 95 ℃ of USSR (Union of Soviet Socialist Republics) and report with aluminium-titanium-zirconium tanning agent, to the physical and mechanical properties of upper leather and the influence of fibrous texture (N.Nishad Fathima, T.Prem Kumar, JALCA, 2006,101:58-65).
People such as Dan Zhihua have invented the method that Chrome-free cleans tanning, characteristics are Tai-Ace S 150, ferric sulfate tanning agent and Syntan Combination Tannage system pig, ox, sheepskin, its shrinkage temperature can reach 110 ℃, outward appearance is near white, good hand feeling softness, good springiness, and have good sweat proof, ageing-resistant, a heat-stable performance, every physical performance index has all reached the company standard (Dan Zhihua of chrome tanned leather standard and domestic and international medium-to-high grade automobile cushion leather manufacturing, Xin Zhongyin. leather science and engineering 2002,12(5): 18-21).But defend China rare earth chloride is applied to achieve good results during pigskin garment leather makes (but defend China, once farsighted. leather chemical industry .2001,18(5): 27-32).
In sum, prior art has the following disadvantages:
1. existing chromium-free metal tanning agent has a variety of, as zirconium, aluminium, titanium, iron, rare earth etc., is difficult to satisfy different performance of leather requirements but use separately.
2. the research of multi-metal complex lacks sufficient theoretical basis, and the many metals that obtain and the mole proportioning of part are not necessarily best.
Summary of the invention
The objective of the invention is provides the many metals of a kind of zirconium-aluminium to cooperate owse and preparation method thereof at the deficiencies in the prior art, is characterized in realizing not having chrome tanned leather, solves the problem of the pollution of chromium the leather industry from the source.
The objective of the invention is to realize that wherein said raw material umber is parts by weight except that specifying by following technical measures:
Zirconium sulfate ZrO
2Content 20 ~ 30% 0.5 ~ 10 part
Tai-Ace S 150 Al
2O
310 ~ 16% 1 ~ 20 part
The effective Han Liang of masking agent ≧ 94% 0.1 ~ 10 part
Masking agent is at least a in sodium formiate, Sodium.alpha.-hydroxypropionate, sodium tartrate, sodium oxalate, Trisodium Citrate or the sodium phthalate.
The many metals of zirconium-aluminium cooperate the preparation method of owse may further comprise the steps:
(1) preparation of zirconium sulfate solution
With zirconium sulfate 0.1 ~ 10 weight part, be that aqueous sulfuric acid 50 ~ 300 weight parts of 0.2 ~ 0.8mol/L are dissolved into solution with concentration;
(2) preparation of alum liquor
With Tai-Ace S 150 1 ~ 20 weight part, be that aqueous sulfuric acid 50 ~ 400 weight parts of 0.2 ~ 0.8mol/L are dissolved into solution with concentration;
(3) preparation of masking agent solution
With masking agent 0.1 ~ 10 parts by volume, become solution with 50 ~ 200 weight part dissolved in distilled water;
(4) cover the preparation of the title complex of limiting
Above-mentioned zirconium sulfate, alum liquor are added and have in the reactor of agitator, under agitation add masking agent solution, and add aqueous sodium hydroxide solution 3 ~ 50 weight parts of 0.05 ~ 1mol/L, the pH value of regulator solution is 1.5 ~ 2.50.Leave standstill 24 ~ 72h after stirring.
The many metals of zirconium-aluminium that obtained by method for preparing cooperate the owse good stability, and precipitation pH value is higher than 3.5.
Sodium hydroxide, sulfuric acid, zirconium sulfate, Tai-Ace S 150 and sodium formiate Sodium.alpha.-hydroxypropionate, sodium tartrate, sodium oxalate, Trisodium Citrate and sodium phthalates etc. all among the present invention are commercial technical pure.
The present invention has the following advantages:
(1) the many metals of zirconium-aluminium cooperate owses and preparation method to having improved the added value of zirconium and aluminum metal resource, and are friendly to environment.
(2) it is suitable that the many metals of zirconium-aluminium cooperate the composition of owse, not only can the conservation consumption, and can also improve the stability of title complex, thereby have good reactivity worth.
(3) in zirconium-aluminium multi-metal complex, add suitable masking agent, help further improving the stability of multi-metal complex, thereby give zirconium-aluminium multi-metal complex with good reactivity worth.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; and 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 according to the content of foregoing invention.
Embodiment 1
(1) preparation of zirconium sulfate solution
With zirconium sulfate solid 0.7 weight part, be that aqueous sulfuric acid 100 weight parts of 0.1mol/L are dissolved into solution with concentration;
(2) preparation of alum liquor
With Tai-Ace S 150 solid 2.5 weight parts, be that aqueous sulfuric acid 200 weight parts of 0.63mol/L are dissolved into solution with concentration;
(3) preparation of sodium citrate solution
With Trisodium Citrate solid 0.6 weight part, become solution with 100 weight part dissolved in distilled water;
(4) Trisodium Citrate covers the preparation of the title complex of limiting
Above-mentioned zirconium sulfate solution, alum liquor and sodium citrate solution are added in the reactor, and regulating the pH value with the sodium hydroxide of 0.1mol/L is 1.5, leaves standstill slaking 24h after stirring.
Embodiment 2
(1) preparation of zirconium sulfate solution
With zirconium sulfate solid 1.4 weight parts, be that aqueous sulfuric acid 200 parts by volume of 0.1mol/L are dissolved into solution with concentration;
(2) preparation of alum liquor
With Tai-Ace S 150 solid 4 weight parts, be that aqueous sulfuric acid 300 parts by volume of 0.63mol/L are dissolved into solution with concentration;
(3) preparation of sodium oxalate sodium solution
With sodium oxalate solid 0.5 weight part, become solution with 200 parts of dissolved in distilled water;
(4) sodium oxalate covers the preparation of the title complex of limiting
Above-mentioned zirconium sulfate solution, alum liquor and sodium oxalate solution are added in the reactor, and regulating the pH value with the sodium hydroxide of 0.1mol/L is 2.0, leaves standstill slaking 24h after stirring.
Embodiment 3
(1) preparation of zirconium sulfate solution
With zirconium sulfate solid 1 weight part, be that aqueous sulfuric acid 150 parts by volume of 0.1mol/L are dissolved into solution with concentration;
(2) preparation of alum liquor
With Tai-Ace S 150 solid 1.3 weight parts, be that aqueous sulfuric acid 100 parts by volume of 0.63mol/L are dissolved into solution with concentration;
(3) preparation of sodium lactate solution
With Sodium.alpha.-hydroxypropionate solid 0.7 weight part, become solution with 300 parts of dissolved in distilled water;
(4) Sodium.alpha.-hydroxypropionate covers the preparation of the title complex of limiting
Above-mentioned zirconium sulfate solution, alum liquor and sodium lactate solution are added in the reactor, and regulating the pH value with the sodium hydroxide of 0.1mol/L is 2.5, leaves standstill slaking 24h after stirring.
Application example 1
The many metals of zirconium-aluminium cooperate the technology of owse tanning ox-hide, and the deashing and softening ox-hide that obtains with conventional method for leather-making is a raw material, is undertaken by following technology:
(1) pickling:
1.. technical stipulation: liquor ratio 5-7, interior temperature 20-25 ℃, sulfuric acid (98%) 0.5-0.8g/L, salt 80g/L, formic acid (85%) 2 ~ 3 g/L.
2.. working method: mix up liquor ratio, interior temperature in accordance with regulations, add the salt of specified amount earlier, require to reach more than 8 ° of B é.Add the formic acid that diluted with 8-10 times of normal-temperature water in advance from drum gudgeon in the rotation, add the sulfuric acid that diluted with 10 ~ 15 times of normal-temperature water in advance again, rotate 2 ~ 4h, require terminal point pH2.0 ~ 2.4.
(2) oily pretan
1.. technical stipulation: in above-mentioned pickling liquid, carry out sulfited fish oil: 2 ~ 3g/L.
2.. working method: after above-mentioned pickling reaches requirement, use 50 ~ 70 ℃ of warm water emulsive sulfited fish oils of 5 ~ 10 times in advance, rotate 30min.
(3) zirconium-aluminum tanning system
1.. technical stipulation: above-mentioned have in the oily pretan waste liquid carry out zirconium-aluminium multi-metal complex owse: 12 ~ 20g/L; Sodium.alpha.-hydroxypropionate: 3 ~ 5g/L; Sodium bicarbonate: 4g/L; Liquor ratio is 5 ~ 6; Temperature: normal temperature.
2.. working method: after above-mentioned oily pretan reached requirement, temperature was a normal temperature, and the concentration requirement of salt reaches 8 ° of B é, if inaccessible words add salt and regulate.Then, add earlier half many metals of zirconium-aluminium of total amount and cooperate owse, Sodium.alpha.-hydroxypropionate, rotate 90 ~ 120min, add remaining many metals of zirconium-aluminium owse and Sodium.alpha.-hydroxypropionate again, rotate 90 ~ 120min.The inspection situation of tanning, begin to carry alkali after tanning, putting forward the alkali operation steps is that first warm water with 15-20 times 30-35 ℃ dissolves sodium bicarbonate fully, divides 6-8 adding, the each rotation 20 minutes, add the back and rotated 90 minutes, require pH3.6 ~ 4.0, standing over night, rotated next day 30 minutes, add hot water (55 ~ 60 ℃) and be warming up to 36 ℃, make liquor ratio reach 5 ~ 6, rotate 240min.Tanning total time 48h.
(4) leave standstill: take horse and left standstill 2-3 days.
Subsequent operations technology is routinely carried out.
Application example 2
The technology of zirconium-aluminium multi-metal complex powder tanning goatskin, the deashing and softening lamb skin that obtains with conventional method for leather-making is a raw material, is undertaken by following technology:
(1) pickling:
1.. technical stipulation: liquor ratio 20-25, interior temperature 20-25 ℃, sulfuric acid (98%) 0.5-0.8 g/L, salt 80 g/L, formic acid (85%) 3 ~ 5 g/L.
2.. working method: mix up liquor ratio, interior temperature in accordance with regulations, add the salt of specified amount earlier, require to reach more than 8 ° of B é.Add the formic acid that diluted with 8-10 times of normal-temperature water in advance from rotary drum drum axle in the rotation, add the sulfuric acid that diluted with 10 ~ 15 times of normal-temperature water in advance again, rotate 2 ~ 4h, require terminal point pH2.0 ~ 2.5.
(2) oily pretan
1.. technical stipulation: in above-mentioned pickling liquid, carry out sulfited fish oil: 3 ~ 4 g/L.
2.. working method: after above-mentioned pickling reaches requirement, use 50 ~ 70 ℃ of warm water emulsive sulfited fish oils of 5 ~ 10 times in advance, rotate 30min.
(3) zirconium-aluminum tanning system
1.. technical stipulation: in above-mentioned oily pretan waste liquid, carry out zirconium-aluminium multi-metal complex owse: 20 ~ 25 g/L; Trisodium Citrate: 5 ~ 7 g/L; Sodium bicarbonate: 3 ~ 4 g/L; Liquor ratio is: 5 ~ 6; Temperature: normal temperature.
2.. working method: after above-mentioned oily pretan reaches requirement, in the pickling waste liquid, carry out, temperature is a normal temperature, the concentration requirement of salt reaches 8 ° of B é, add earlier half many metals of zirconium-aluminium of total amount and cooperate owse, Trisodium Citrate, rotate 90 ~ 120min, add remaining many metals of zirconium-aluminium owse and Trisodium Citrate again, rotate 90 ~ 120min.The inspection situation of tanning, begin to carry alkali after tanning, putting forward the alkali operation steps is that first warm water with 15-20 times 30-35 ℃ dissolves sodium bicarbonate fully, divides 6-8 adding, the each rotation 20 minutes, add the back and rotated 90 minutes, require pH3.6 ~ 3.8, standing over night, rotated next day 30 minutes, measure shrinkage temperature and add hot water (55 ~ 60 ℃) and be warming up to 36 ℃, make liquor ratio reach 5, rotate 240min after.Tanning total time 48h.
(4) leave standstill: take horse and left standstill 2-3 days.
Subsequent operations technology is routinely carried out.
Application example 3
The many metals of zirconium-aluminium cooperate the technology of owse tanning pigskin, and the deashing and softening pigskin that obtains with conventional method for leather-making is a raw material, is undertaken by following technology:
(1) pickling:
1.. technical stipulation: liquor ratio 0.5-0.8, interior temperature 20-25 ℃, sulfuric acid (98%) 0.5-0.8g/L, salt 60g/L, formic acid (85%) 3 ~ 4 g/L.
2.. working method: mix up liquor ratio, interior temperature in accordance with regulations, add the salt of specified amount earlier, require to reach more than 8 ° of B é.Add the formic acid that diluted with 8-10 times of normal-temperature water in advance from rotary drum drum axle in the rotation, add the sulfuric acid that diluted with 10 ~ 15 times of normal-temperature water in advance again, rotate 2h, require terminal point pH2.4 ~ 2.8.
(2) oily pretan
1.. technical stipulation: in above-mentioned pickling liquid, carry out sulfited fish oil: 2 ~ 2.5g/L.
2.. working method: after above-mentioned pickling reaches requirement, use 50 ~ 70 ℃ of warm water emulsive sulfited fish oils of 5 ~ 10 times in advance, rotate 30min.
(3) zirconium-aluminum tanning system
1.. technical stipulation: in above-mentioned oily pretan waste liquid, carry out zirconium-aluminium multi-metal complex owse: 15 ~ 20g/L; Trisodium Citrate: 3 ~ 5 g/L; Sodium bicarbonate: 4 ~ 5 g/L; Liquor ratio is: 5 ~ 6; Temperature: normal temperature.
2.. working method: after above-mentioned oily pretan reaches requirement, in the pickling waste liquid, carry out, temperature is a normal temperature, the concentration requirement of salt reaches 8 ° of B é, add earlier half many metals of zirconium-aluminium of total amount and cooperate owse, Trisodium Citrate, rotate 90 ~ 120min,, rotate 90 ~ 120min adding remaining many metals of zirconium-aluminium owse and Trisodium Citrate.The inspection situation of tanning, begin to carry alkali after tanning, the operation steps of carrying alkali is that first warm water with 15-20 times 30-35 ℃ dissolves sodium bicarbonate fully, divides 6-8 adding, the each rotation 20 minutes, add the back and rotated 90 minutes, require pH3.8 ~ 4.0, standing over night, rotated next day 30 minutes, measure shrinkage temperature and add hot water (55 ~ 60 ℃) and be warming up to 36 ℃, make liquor ratio reach 5, rotate 240min.Tanning total time 48h.
(4) leave standstill: take horse and left standstill 2-3 days.
Subsequent operations technology is routinely carried out.
Claims (2)
1. zirconium-aluminium multi-metal complex owse is characterized in that the recipe ingredient of this title complex owse is by weight:
Zirconium sulfate ZrO
2Content 20 ~ 30% 5 ~ 20 part
Tai-Ace S 150 Al
2O
310 ~ 16% 20 ~ 80 part
Masking agent effective content 〉=95% 0.5 ~ 10 part
Zirconium-aluminium multi-metal complex owse according to claim 1 is characterized in that described masking agent is at least a in sodium formiate, Sodium.alpha.-hydroxypropionate, sodium tartrate, sodium oxalate, Trisodium Citrate or the sodium phthalate.
2. preparation method who adopts the described zirconium of claim 1-aluminium multi-metal complex owse is characterized in that this method may further comprise the steps:
(1) preparation of zirconium sulfate solution
With zirconium sulfate 5 ~ 20 weight parts, be that aqueous sulfuric acid 50 ~ 300 weight parts of 0.2 ~ 0.8mol/L are dissolved into solution with concentration;
(2) preparation of alum liquor
With Tai-Ace S 150 20 ~ 80 weight parts, be that aqueous sulfuric acid 50 ~ 400 body weight parts of 0.2 ~ 0.8mol/L are dissolved into solution with concentration;
(3) preparation of masking agent solution
With masking agent 0.5 ~ 10 weight part, become solution with 10 ~ 100 weight part dissolved in distilled water;
(4) cover the preparation of the title complex of limiting
Above-mentioned zirconium sulfate, alum liquor are added and have in the reactor of agitator, under agitation add masking agent solution, and adding aqueous sodium hydroxide solution 1 ~ 10 weight part of 0.05 ~ 1mol/L, the pH value of regulator solution is 1.5 ~ 2.5, leaves standstill 24 ~ 72h after stirring.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719571A (en) * | 2012-06-12 | 2012-10-10 | 陕西科技大学 | Method for preparing aluminum-containing tannins |
| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
| CN103194548A (en) * | 2013-04-22 | 2013-07-10 | 四川大学 | Zirconium-aluminum-titanium tannage waterproof clothing leather and making method thereof |
| CN103469312A (en) * | 2013-08-19 | 2013-12-25 | 佛山捷利再生科技有限公司 | Environment-friendly leather pulp belt material and production technology thereof |
| CN103980304A (en) * | 2014-05-14 | 2014-08-13 | 陕西科技大学 | Chromium-free tanning agent and preparation method thereof |
| CN105624341A (en) * | 2016-01-29 | 2016-06-01 | 佛山市聚成生化技术研发有限公司 | Full grain leather tanning method based on iron tanning agent |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719571A (en) * | 2012-06-12 | 2012-10-10 | 陕西科技大学 | Method for preparing aluminum-containing tannins |
| CN102719571B (en) * | 2012-06-12 | 2014-10-29 | 陕西科技大学 | Method for preparing aluminum-containing tannins |
| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
| CN103194548A (en) * | 2013-04-22 | 2013-07-10 | 四川大学 | Zirconium-aluminum-titanium tannage waterproof clothing leather and making method thereof |
| CN103194548B (en) * | 2013-04-22 | 2016-10-26 | 四川大学 | A kind of Zirconium-aluminum-titanium tan waterproof garment leather and preparation method thereof |
| CN103469312A (en) * | 2013-08-19 | 2013-12-25 | 佛山捷利再生科技有限公司 | Environment-friendly leather pulp belt material and production technology thereof |
| CN103469312B (en) * | 2013-08-19 | 2016-03-02 | 佛山捷利再生科技有限公司 | A kind of environment-friendlyleather leather pulp belt material and production technology thereof |
| CN103980304A (en) * | 2014-05-14 | 2014-08-13 | 陕西科技大学 | Chromium-free tanning agent and preparation method thereof |
| CN105624341A (en) * | 2016-01-29 | 2016-06-01 | 佛山市聚成生化技术研发有限公司 | Full grain leather tanning method based on iron tanning agent |
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Application publication date: 20111005 |