CN103290151B - Method for preparing leather by using chromium-free retanning agent - Google Patents
Method for preparing leather by using chromium-free retanning agent Download PDFInfo
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Abstract
The present invention relates to a method for preparing leather by using a chromium-free retanning agent, and belongs to the technical field of leather treatments. In order to solve defects of heavy chromium pollution, low shrinkage temperature, and low precipitation point during a retanning process, a method for preparing leather by using a chromium-free retanning agent is provided. The method comprises: adding shaving leather to a rotation drum, adding 100-150 wt% of water, adjusting a temperature to 25-30 DEG C, adding 1.5-2.0 wt% of a coordination polymer Inhibitor, rotating for 10-30 min, adjusting the pH value of a bath liquid to less than or equal to 3.5, rotating for 60-90 min, adding 1.0-2.0 wt% of auxiliary tanning tannin, rotating for 90-120 min, adding a non-chromium metal composite tanning agent and 0.2-0.4 wt% of an alkali extraction agent to carry out alkali extraction, heating to a temperature of 38-40 DEG C to carry out a treatment, and carrying out a post-treatment to prepare the leather finished product. The method has advantages of high tannin agent precipitation point and high shrinkage temperature. With the method, the total chromium content of wastewater and sludge can be effectively controlled.
Description
Technical field
The present invention relates to a kind of method without chromium retanning agent process hides, belong to leather processing technology field.
Background technology
In modern tanning industry, chrome tanning agent is the most outstanding a kind of metal-salt tanning agent of application performance, is used widely and dominate in tanning industry.But well-known, chromium is the heavy metal that a kind of meeting brings environmental pollution, general biochemical method is difficult to degraded, usually can gather in the environment, long-term uncontrolled discharge will cause water pollution, affect hydrobiont and microbial growth, destroy the eubiosis, be unfavorable for self purification of water body; And, although leather tanning uses trivalent chromium, also exist in the environment and generate hypertoxic chromic potentially dangerous.
And in existing leather sector, use the operation of chrome tanning agent mainly to comprise chrome tanning and chrome retanned two operations, wherein, chrome tanning is placed on independently tanning process, and waste tanning liquor is easy to shunting, process and reuse, but chrome retanned is then incorporate wet finishing workshop section into.
Chrome retanned almost carries out on the chrome tanning basis of chromium saturated absorption at leather, and chrome uptake rate is low and high by eluting rate theoretically, and the utilization ratio of common chrome retanned technique chromium only has an appointment 50%.The waste liquid that the wet ornamenting operations such as chrome retanned and follow-up neutralization filling, dyeing and fat-liquoring are formed all may contain chromium, we had once carried out tracking and testing to the total chrome content that middle chrome retanned and each master operation waste water of follow-up wet finishing workshop section are criticized in the single production of enterprise, result confirms that chrome retanned waste liquid itself has the chromium existence of high level, and neutralization is filled, dyeing and fat-liquoring operation also has part chromium by wash-out out.Due to chrome retanned and follow-up wet ornamenting have that operation is many, waste liquid complicated components and shunting difficulty, the chromate waste water causing these operations to be formed enters composite wastewater, chromium after treatment in waste water forms chromium hydroxide precipitation and enters comprehensive mud, makes the total chrome content of comprehensive mud higher.
On the other hand, at present existingly the organic tanning agent based on aldehyde tannage mechanism, the combination tanning agent based on synthetic tanning agent, other organic tanning agents and chrome-free metal composite tanning agent is mainly comprised without chrome tanning tanning agent.Although adopt aldehyde tanning agent mainly to utilize aldehyde material and modified product thereof, environmental pollution is little, can implement salt-free not pickling, but have that grain is partially thick, reduced scale, containing shortcomings such as free formaldehydes; Although and adopt synthetic tanning agent shrinkage temperature higher, soft and full property shortcoming, leather style is limited, and in waste water, aldehyde is higher affects biochemical treatment, and the matching of the two and chrome tanning process is slightly poor, need strengthen the exploitation of supplementary material; And adopt chrome-free metal composite tanning agent process leather shrinking temperature higher, good with the matching of a whole set of the comparatively perfect leather-making technology formed based on chromic tanning and material, its shortcoming is that tanning agent set point is lower.
Summary of the invention
The present invention is directed to the defect existed in above prior art, a kind of method without chromium retanning agent process hides is provided, can achieve effective control chromium metal content and the effect improving tanning agent set point and leather shrinking temperature.
The object of the invention is to be achieved by the following technical programs, a kind of method without chromium retanning agent process hides, the method comprises the following steps:
A, add in rotary drum by chrome tanning shaving leather, then, then add the water of chrome tanning shaving leather weight 100wt% ~ 150wt%, adjustment temperature to 25 DEG C ~ 30 DEG C, what add chrome tanning shaving leather weight 1.5wt% ~ 2.0wt% joins polygalacturonase inhibitor, rotates 10min ~ 30min;
B, regulate the pH value of body lotion to≤3.5 with sulfuric acid again, rotate 60min ~ 90min;
C, add chrome tanning shaving leather weight 1.0wt% ~ 2.0wt% help tannin of tanning, rotate 90min ~ 120min;
D, add the chrome-free metal composite tanning agent of chrome tanning shaving leather weight 3.5wt% ~ 4.0wt%, rotate 180min ~ 210min, then the compound adding chrome tanning shaving leather weight 0.2wt% ~ 0.4wt% is carried alkaline agent and carried out carrying alkali, carrying the alkali time is 180min ~ 210min;
E, be warming up to 38 DEG C ~ 40 DEG C again and carry out process 90min ~ 120min, stop drum and spend the night, go out that drum is taken horse, left standstill, dyeing and finishing, covering with paint, make finished leather.
The present invention adopts the retanning of chrome-free metal composite tanning agent system, advantages, and the existing shortcoming existed when just tanning is weakened, and can play the effect of mutual supplement with each other's advantages with chrome tanning agent; Meanwhile, be with the weighing scale weight of chrome tanning shaving leather during retanning, the consumption of chrome-free metal composite tanning agent than be used in just tan few a lot, less to cost impact; When the present invention adopts chrome-free metal composite tanning agent retanning, the specific absorption of tanning agent is high, far above chrome uptake rate during chrome retanned, and higher by the leather shrinking temperature of this tanning agent process; Shaving, napping are effective, and fine hair is thin, short, close and comparatively even; Leather is resistance to deposit with ageing-resistant performance good; With a whole set of the comparatively perfect leather-making technology formed based on chromic tanning and material system matching good.But on the other hand, owing to adopting chrome-free metal composite tanning agent to there is the lower defect of set point, when being used alone, system pH is slightly high will coordination, even precipitates.Therefore, the present invention is by first adding the coordination of joining polygalacturonase inhibitor and suppressing chrome-free metal composite tanning agent at the retanning initial stage, improve its set point, and then turn down pH value, make the requirement fully meeting retanning process, the active group avoiding tanning agent and collagen is combined in surface prematurely, makes tanning agent can be slowly uniform to intradermal penetration.After add and help tannin of tanning, this help tan tannin and non-chromium metal tanning agent substantially inoperative, but the retanning later stage can promote to help tan tannin and chrome-free metal composite tanning agent to play and act synergistically, strengthen the combination of tanning agent and leather, shrinkage temperature and the over-all properties of leather can be improved, in fullness ratio, be also better than chrome retanned leather, embody the advantage without chrome retanned, realize the superior of Chrome-free retanned leather.
In the above-mentioned method without chromium retanning agent process hides, as preferably, many metal composite tanning agent of the selected among zirconium of chrome-free metal composite tanning agent described in step D tanning agent, aluminum tanning agent and titanium tannage agent compound.Adopt this composite tanning agent material therefor to meet environmental requirement, and the specific absorption of retanning agent (in zirconium tanning agent) is up to more than 90%, far above chrome uptake rate during chrome retanned, and the leather shrinking temperature higher (reaching more than 95 DEG C) of process.As further preferred, in described many metal composite tanning agent, the content of zirconium is (with ZrO
2meter)>=25%.As further preferred, zirconium tanning agent in described many metal composite tanning agent: aluminum tanning agent: the mass ratio of titanium tannage agent is 1:0.2 ~ 0.4:0.1 ~ 0.2.
In the above-mentioned method without chromium retanning agent process hides, described in join polygalacturonase inhibitor and have another name called without chrome tanning companion.As preferably, joining polygalacturonase inhibitor described in steps A is the mixture with different carboxylic acids class material.Further preferably, described in join polygalacturonase inhibitor for joining polygalacturonase inhibitor D8, its key technical indexes is: solid content >=48%, and pH (10% aqueous solution) 4.0 ~ 7.0, can be miscible with arbitrary proportion with water, and outward appearance is the pale yellow transparent aqueous solution.Non-chromium metal retanning agent effectively can be suppressed to produce precipitation because of coordination, the set point of tanning agent can be significantly improved, contribute to the infiltration of tanning agent in leather, promote that chrome-free tanning agent is more evenly distributed in leather, make grain more carefully flat.In particular, what this joined that polygalacturonase inhibitor can avoid the active group of tanning agent and collagen too early is combined in surface, makes tanning agent can be slowly uniform to intradermal penetration.Although, adopt single compound such as lactic acid, acetic acid etc. also can improve the set point of chrome-free metal composite tanning agent, DeGrain, the partially flat shortcoming such as thin of tanning.And the present invention adopts joins polygalacturonase inhibitor, the APEO do not limited the use of containing EU Committee and aldehyde material.And there is good acidproof, electrolyte-resistant and the salt-stable of resistance to Tanning Metal, non-chromium metal tanning agent can be effectively suppressed to produce precipitation because of coordination, the set point of tanning agent can be significantly improved, contribute to the infiltration of tanning agent in leather, promote that non-chromium metal tanning agent is more evenly distributed in leather, make the grain side of leather of non-chromium metal tanning agent tanning more carefully flat, and it is larger to join polygalacturonase inhibitor consumption, grain side of leather is carefully more flat, but the amount added is too much, and the shrinkage temperature of leather can be made to decline.Visible, non-chromium metal tanning agent of the present invention with join polygalacturonase inhibitor there is good synergy, can realize improving the set point of chrome-free metal composite tanning agent and ensureing the effect of leather shrinking temperature simultaneously.
In the method for above-mentioned chrome-tanned bovine leather without chrome retanned process hides, as preferably, the tannin of tanning of helping described in step C is low flexibility improved plant tannin.Shrinkage temperature and the over-all properties of leather can be improved.As further preferably, described low flexibility improved plant tannin is selected from the low flexibility tannin of VPN, can strengthen the combination of tanning agent and leather, the flexibility of raising leather and sense of fullness for metal without the pretan of chrome tanning leather.Give the light color and luster of leather and good photostabilization.
In the method for above-mentioned chrome-tanned bovine leather without chrome retanned process hides, as preferably, compound described in step D carries alkaline agent mainly containing hydrated magnesium.The combination of tanning agent and collagen can be promoted; and this to put forward alkaline agent self pH value lower, effect relaxes, and surge capability is strong; when can prevent from using, local ph is too high and cause leather be off color normal or produce the defect of chromium spot; can production operation be simplified, meanwhile, adopt this compound to carry alkaline agent and eliminate the Carbon emission problem brought when adopting sodium bicarbonate to carry alkali; belong to without carbon products; meet environmental requirement, alkalinization to metal tanning agents can be completed in the short period, put forward alkali controllability than magnesium oxide better.As further preferred, it is that BBA-2 type high efficiency composition carries alkaline agent that described compound carries alkaline agent.This technical indicator carrying alkaline agent is: Suan Rong Liang≤25moL/kg, appearance white pulverulent solids.
In sum, the present invention has the following advantages:
1. chrome-tanned bovine leather of the present invention is without the method for chrome retanned process hides, adopt non-chromium metal retanning agent, effectively can solve the pollution of chromium ion during retanning, meet the requirement of environmental protection, and adopt join polygalacturonase inhibitor and non-chromium metal retanning agent with the use of, there is synergy, then by control ph, the effect improving set point and leather shrinking temperature can be realized simultaneously.
2. chrome-tanned bovine leather of the present invention is without the method for chrome retanned process hides, preferably adopts compound to carry alkaline agent mainly containing hydrated magnesium.The combination of tanning agent and collagen can be promoted; and this to put forward alkaline agent self pH value lower; effect relaxes; surge capability is strong; when can prevent from using, local ph is too high and cause leather be off color normal or produce the defect of chromium spot; alkalinization to metal tanning agents can be completed in the short period, put forward alkali controllability than magnesium oxide better.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited to these embodiments.
Embodiment 1
Chrome tanning shaving leather is dropped into rotary drum, again using the weight of chrome tanning shaving leather as the batching foundation of following composition, add the water of the 150wt% of chrome tanning shaving leather weight, the weight ratio (g) being equivalent to weight (g) and the water that chrome tanning shaving is removed from office is 1:1.5, then temperature adjustment to 25 DEG C, add and join polygalacturonase inhibitor 1.5%, rotate 15min; Add pH≤3.5 that sulfuric acid regulates body lotion again, rotate 60min; What add chrome tanning shaving leather weight 1.0wt% again helps tannin of tanning, then, after rotating 120min, the non-chromium metal compound adding chrome tanning shaving leather weight 4.0wt% is tanned, described chrome-free metal composite tanning agent is many metal composite tanning agent of zirconium tanning agent, aluminum tanning agent and titanium tannage agent compound, rotates 180min; Finally, the compound adding chrome tanning shaving leather weight 0.3wt% is carried alkaline agent and is carried out carrying alkali, carries alkali time 210min, makes the control of the pH uniformity of body lotion 4.0 ~ 4.2; Carry after alkali terminates, then be warming up to 38 DEG C ~ 40 DEG C, after rotating 120min, stop drum and spend the night; Next day turns 30min again, go out drum and take horse, then technique carries out follow-up dyeing and finishing process routinely, finished product leather.The specific absorption (in zirconium tanning agent) of the tanning agent described in the method reaches more than 90%, and the shrinkage temperature of the leather obtained is higher, reaches more than 95 DEG C, and the set point of tanning agent is greater than 4.5.
Embodiment 2
Chrome tanning shaving leather is dropped into rotary drum, again using the weight of chrome tanning shaving leather as the batching foundation of following composition, add the water of the 100wt% of chrome tanning shaving leather weight, the weight ratio (g) being equivalent to weight (g) and the water that chrome tanning shaving is removed from office is 1:1, then temperature adjustment to 30 DEG C, add and join polygalacturonase inhibitor 2.0%, rotate 10min; Add pH≤3.5 that sulfuric acid regulates body lotion again, rotate 90min; What add chrome tanning shaving leather weight 2.0wt% again helps tannin of tanning, then, after rotating 90min, the non-chromium metal compound adding chrome tanning shaving leather weight 3.5wt% is tanned, described chrome-free metal composite tanning agent is many metal composite tanning agent of zirconium tanning agent, aluminum tanning agent and titanium tannage agent compound, rotates 210min; Finally, the compound adding chrome tanning shaving leather weight 0.2wt% is carried alkaline agent and is carried out carrying alkali, carries alkali time 190min, makes the control of the pH uniformity of body lotion 4.0 ~ 4.2; Carry after alkali terminates, then be warming up to 40 DEG C, after rotating 90min, stop drum and spend the night; Next day turns 30min again, go out drum and take horse, then technique carries out follow-up dyeing and finishing process routinely, prepares finished leather.The specific absorption (in zirconium tanning agent) of the tanning agent described in the method reaches more than 90%, and the shrinkage temperature of the leather obtained is higher, reaches more than 95 DEG C, and the set point of tanning agent is greater than 4.5.
Embodiment 3
Chrome tanning shaving leather is dropped into rotary drum, again using the weight of chrome tanning shaving leather as the batching foundation of following composition, add the water of the 120wt% of chrome tanning shaving leather weight, the weight ratio (g) being equivalent to weight (g) and the water that chrome tanning shaving is removed from office is 1:1.2, then temperature adjustment to 28 DEG C, add and join polygalacturonase inhibitor 1.8%, rotate 15min; Add pH≤3.5 that sulfuric acid regulates body lotion again, rotate 80min; What add chrome tanning shaving leather weight 1.5wt% again helps tannin of tanning, then, after rotating 100min, the non-chromium metal compound adding chrome tanning shaving leather weight 3.8wt% is tanned, described chrome-free metal composite tanning agent is many metal composite tanning agent of zirconium tanning agent, aluminum tanning agent and titanium tannage agent compound, in described many metal composite tanning agent, the mass percent of zirconium tanning agent is 30%, rotates 200min; Finally, the compound adding chrome tanning shaving leather weight 0.3wt% is carried alkaline agent and is carried out carrying alkali, carries alkali time 180min, makes the control of the pH uniformity of body lotion 4.0 ~ 4.2; Carry after alkali terminates, then be warming up to 38 DEG C, after rotating 110min, stop drum and spend the night; Next day turns 30min again, go out drum and take horse, then technique carries out follow-up dyeing and finishing process routinely, finished product leather.The specific absorption (in zirconium tanning agent) of the tanning agent described in the method reaches more than 90%, and the shrinkage temperature of the leather obtained is higher, reaches more than 95 DEG C, and the set point of tanning agent is greater than 4.5.
Embodiment 4
Chrome tanning shaving leather is dropped into rotary drum, again using the weight of chrome tanning shaving leather as the batching foundation of following composition, add the water of the 130wt% of chrome tanning shaving leather weight, the weight ratio (g) being equivalent to weight (g) and the water that chrome tanning shaving is removed from office is 1:1.3, then temperature adjustment to 30 DEG C, add and join polygalacturonase inhibitor 2.0%, described polygalacturonase inhibitor of joining preferably adopts the mixture with different carboxylic acids class material, rotates 10min; Add pH≤3.5 that sulfuric acid regulates body lotion again, rotate 90min; What add chrome tanning shaving leather weight 1.8wt% again helps the low flexibility tannin of the tannin VPN that tans, then, after rotating 90min, add the chrome-free metal composite tanning agent of chrome tanning shaving leather weight 3.8wt%, described chrome-free metal composite tanning agent is many metal composite tanning agent of zirconium tanning agent, aluminum tanning agent and titanium tannage agent compound, content >=25% of zirconium in described many metal composite tanning agent, rotates 210min; Finally, the compound adding chrome tanning shaving leather weight 0.3wt% is carried alkaline agent and is carried out carrying alkali, described in carry alkaline agent mainly containing hydrated magnesium, carry alkali time 190min, make the control of the pH uniformity of body lotion 4.0 ~ 4.2; Carry after alkali terminates, then be warming up to 40 DEG C, after rotating 90min, stop drum and spend the night; Next day turns 30min again, go out drum and take horse, then technique carries out follow-up dyeing and finishing process routinely, prepares finished leather.The specific absorption (in zirconium tanning agent) of the tanning agent described in the method reaches more than 90%, and the shrinkage temperature of the leather obtained is higher, reaches more than 95 DEG C, and the set point of tanning agent is greater than 4.5.
Embodiment 5
Chrome tanning shaving leather is dropped into rotary drum, again using the weight of chrome tanning shaving leather as the batching foundation of following composition, add the water of the 140wt% of chrome tanning shaving leather weight, the weight ratio (g) being equivalent to weight (g) and the water that chrome tanning shaving is removed from office is 1:1.4, then temperature adjustment to 30 DEG C, add and join polygalacturonase inhibitor 1.8%, described polygalacturonase inhibitor of joining preferably adopts the mixture with different carboxylic acids class material, rotates 10min; Add pH≤3.5 that sulfuric acid regulates body lotion again, rotate 90min; What add chrome tanning shaving leather weight 2.0wt% again helps the low flexibility tannin of the tannin VPN that tans, then, after rotating 90min, add the chrome-free metal composite tanning agent of chrome tanning shaving leather weight 3.8wt%, described chrome-free metal composite tanning agent is many metal composite tanning agent of zirconium tanning agent, aluminum tanning agent and titanium tannage agent compound, zirconium tanning agent in described many metal composite tanning agent: aluminum tanning agent: the mass ratio of titanium tannage agent is 1:0.2:0.2, rotates 210min; Finally, the compound adding chrome tanning shaving leather weight 0.3wt% is carried alkaline agent and is carried out carrying alkali, described in carry alkaline agent mainly containing hydrated magnesium, carry alkali time 190min, make the control of the pH uniformity of body lotion 4.0 ~ 4.2; Carry after alkali terminates, then be warming up to 40 DEG C, after rotating 90min, stop drum and spend the night; Next day turns 30min again, go out drum and take horse, then technique carries out follow-up dyeing and finishing process routinely, prepares finished leather.The specific absorption (in zirconium tanning agent) of the tanning agent described in the method reaches more than 90%, and the shrinkage temperature of the leather obtained is higher, reaches more than 95 DEG C, and the set point of tanning agent is greater than 4.5.
Embodiment 6
Chrome tanning shaving leather is dropped into rotary drum, again using the weight of chrome tanning shaving leather as the batching foundation of following composition, add the water of the 150wt% of chrome tanning shaving leather weight, the weight ratio (g) being equivalent to weight (g) and the water that chrome tanning shaving is removed from office is 1:1.5, then temperature adjustment to 25 DEG C, add and join polygalacturonase inhibitor 1.5%, described polygalacturonase inhibitor of joining preferably adopts the mixture with different carboxylic acids class material, rotates 10min; Add pH≤3.5 that sulfuric acid regulates body lotion again, rotate 90min; Add the low flexibility improved plant tannin of chrome tanning shaving leather weight 1.6wt% again, and not containing pigment, then, after rotating 90min, add the chrome-free metal composite tanning agent of chrome tanning shaving leather weight 4.0wt%, described chrome-free metal composite tanning agent is many metal composite tanning agent of zirconium tanning agent, aluminum tanning agent and titanium tannage agent compound, zirconium tanning agent in described many metal composite tanning agent: aluminum tanning agent: the mass ratio of titanium tannage agent is 1:0.3:0.1, rotates 210min; Finally, the compound adding chrome tanning shaving leather weight 0.3wt% is carried alkaline agent and is carried out carrying alkali, described in carry alkaline agent mainly containing hydrated magnesium, carry alkali time 190min, make the control of the pH uniformity of body lotion 4.0 ~ 4.2; Carry after alkali terminates, then be warming up to 40 DEG C, after rotating 90min, stop drum and spend the night; Next day turns 30min again, go out drum and take horse, then technique carries out follow-up dyeing and finishing process routinely, prepares finished leather.The specific absorption (in zirconium tanning agent) of the tanning agent described in the method reaches more than 90%, and the shrinkage temperature of the leather obtained is higher, reaches more than 95 DEG C, and the set point of tanning agent is greater than 4.5.
Specific embodiment described in the present invention is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Although made a detailed description the present invention and quoted some specific embodiments as proof, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (5)
1. without a method for chromium retanning agent process hides, it is characterized in that, the method comprises the following steps:
A, add in rotary drum by chrome tanning shaving leather, then, then add the water of chrome tanning shaving leather weight 100wt% ~ 150wt%, adjustment temperature to 25 DEG C ~ 30 DEG C, what add chrome tanning shaving leather weight 1.5wt% ~ 2.0wt% joins polygalacturonase inhibitor, rotates 10min ~ 30min; Described polygalacturonase inhibitor of joining is the mixture with different carboxylic acids class material, and described in join polygalacturonase inhibitor for joining polygalacturonase inhibitor D8;
B, regulate the pH value of body lotion to≤3.5 with sulfuric acid again, rotate 60min ~ 90min;
C, add chrome tanning shaving leather weight 1.0wt% ~ 2.0wt% low flexibility improved plant tannin, rotate 90min ~ 120min;
D, add chrome tanning shaving leather weight 3.5wt% ~ 4.0wt% chrome-free metal composite tanning agent, rotate 180min ~ 210min, the compound adding chrome tanning shaving leather weight 0.2wt% ~ 0.4wt% is again carried alkaline agent and is carried out carrying alkali, and carrying the alkali time is 180min ~ 210min;
E, be warming up to 38 DEG C ~ 40 DEG C again and carry out process 90min ~ 120min, stop drum and spend the night, go out that drum is taken horse, left standstill, dyeing and finishing, covering with paint, make finished leather.
2. according to the method for claim 1 without chromium retanning agent process hides, it is characterized in that, many metal composite tanning agent of the selected among zirconium of chrome-free metal composite tanning agent described in step D tanning agent, aluminum tanning agent and titanium tannage agent compound.
3. according to claim 2 without the method for chromium retanning agent process hides, it is characterized in that, content >=25% of zirconium in described many metal composite tanning agent.
4. according to claim 1 without the method for chromium retanning agent process hides, it is characterized in that, compound described in step D carries alkaline agent mainly containing hydrated magnesium.
5. according to claim 3 without the method for chromium retanning agent process hides, it is characterized in that, described low flexibility improved plant tannin is selected from the low flexibility tannin of VPN.
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| CN104212921B (en) * | 2014-09-19 | 2016-06-29 | 桐乡市新时代皮草有限公司 | Thin assorted skin chrome retanned method |
| CN106191338B (en) * | 2016-07-29 | 2018-09-18 | 海宁皮革研究院 | A kind of chrome-free metal composite tanning agent is used for the leather-making technology of retanning |
| CN109593895B (en) * | 2018-12-07 | 2021-05-21 | 温州大学 | Modified zirconium-titanium-aluminum complex tanning agent and preparation method thereof |
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Effective date of registration: 20201022 Address after: 317100 Room 1104, Block B, 19 Wutong Road, Haiyou Street, Sanmen County, Taizhou City, Zhejiang Province Patentee after: TAIZHOU YONGXING TRADING Co.,Ltd. Address before: 314400, No. 21, Shi Dao, Haining, Zhejiang, Jiaxing Patentee before: Haining Ruixing Leather Co.,Ltd. Effective date of registration: 20201022 Address after: 215200 No. 1188 west two ring road, Shengze Town, Wujiang District, Suzhou, Jiangsu. Patentee after: Suzhou Shengze science and Technology Pioneer Park Development Co.,Ltd. Address before: 317100 Room 1104, Block B, 19 Wutong Road, Haiyou Street, Sanmen County, Taizhou City, Zhejiang Province Patentee before: TAIZHOU YONGXING TRADING Co.,Ltd. |