CN104726621A - Fur free formaldehyde content reducing method - Google Patents
Fur free formaldehyde content reducing method Download PDFInfo
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- CN104726621A CN104726621A CN201310703427.3A CN201310703427A CN104726621A CN 104726621 A CN104726621 A CN 104726621A CN 201310703427 A CN201310703427 A CN 201310703427A CN 104726621 A CN104726621 A CN 104726621A
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/30—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a fur free formaldehyde content reducing method which comprises the following steps: 1) taking fur for weighing, and determining fur free formaldehyde content; 2) retanning for formaldehyde removal; 3) capturing to remove free formaldehyde; 4) washing to remove the free formaldehyde; 5) dye fixing; and 6) aldehyde fixing. The method can reduce the fur free formaldehyde content from about 450 mg / kg to 70 mg / kg or less, or even 20mg / kg or less, and the fur free formaldehyde content may not significantly rebound within three months.
Description
Technical field
The invention belongs to leather technology field, particularly, relate to a kind of method reducing fur Free-formaldehyde content.
Background technology
Formaldehyde is leather processing, the important chemical feedstocks of one indispensable in especially fur manufacturing process, due to the cost performance that formaldehyde is outstanding, makes to have in many cases use a large amount of formaldehyde.For leather processing, tanning is the core of leather processing, is by chemical reagent and skin protein generation chemical reaction, makes the course of processing that turnover occurs in goods chemical property.
At present can produce tanning effect to skin protein and chrome tanning agent (chromium complex), vegatable tannin and aldehydes tanning agent can be mainly contained by the material (tanning agent) that uses of industrialization.
The net effect of chrome tanning agent tanning is best, but chromium resource is short, and environmental pollution is extremely serious, few chrome tanning, has been the task of top priority without chrome tanning.
In all tanning agents, formaldehyde tanning skin net effect is only second to chrome tanning, and formaldehyde is cheap and easy to get, easy to use, tanning cost is low, particularly water-fastness, the aspect such as sweat proof, antioxidant and reductive agent of the skin of formaldehyde tannage is better than chromed tanned leather, so formaldehyde is widely used in the tanning of fur and the monomer as synthetic tanning agent.
Research shows, in skin formaldehyde and protein bound Four types and separately feature is as follows:
1, physical adsorption, is easy to be washed; 2, be in dynamic chemical equilibrium shape, can change because of medium; 3, stable combination, but be reversible chemically, combination can be reduced by chemical reagent effect; 4, stable and chemical irreversible covalent attachment, antiacid alkali, the effect of chemical resistance reagent.
The formaldehyde being in physical adsorption and dynamic chemical equilibrium state is the formaldehyde source causing free formaldehyde maximum, and from the multiple combining form analysis of formaldehyde and protein, the release of fur goods Free-formaldehyde has chronicity, Retarder theory.
Along with the enhancing day by day of domestic and international human consumer's green consumption consciousness, the danger of some large buyers in order to avoid compensating because some chemical substances in leatherware bring possible negative impact to human body, they are from the limitation regulation of often adding some the special chemical materials leather during developing country's exotic leather, and the situation that exported product meets with Technical Barriers to Trade in importer is of common occurrence.This tendency oneself form and affect the Technical Barriers to Trade that China's leather and leatherware enter world market.
Free formaldehyde be then Technical Barriers to Trade for leather in may one of harmful chemical substance.Free formaldehyde content problem oneself cause the attention of more country, many countries all take strict restriction to formaldehyde content in leather and leather products, to the limit standard of portioned product free formaldehyde in table 1.
Table 1 leather products or clothing Free-formaldehyde limitation
The maturation method that current report solves leather and fur goods free formaldehyde problem is also less, mainly concentrates on the following aspects:
1. improve Process for producing leather, reduce leather and skin free formaldehyde content processed thereof
Liu Xiankui, Wei Na, propose in " summing questions about testing formaldehyde in leather " (Chinese leather, 2004,33 (1): 39-41): (1) adjustment power operation is as water washing operations, drying operation; (2) strengthen power operation, such as strong washing, high drying temperature, increase rotary drum capacity or increase speed of rotation etc., contribute to lowering product Free-formaldehyde content.
2. remove with small molecules free formaldehyde trapping agent or reduce free formaldehyde
Zhu Miaofeng, the gold moonlight is middle proposition following methods in " mensuration of Determination of Formaldehyde in Leather and control " (Chinese leather, 2003,32 (3): 33-34): (1) adds organic formaldehyde scavenger; (2) inorganic formaldehyde scavenger is added; (3) wattle extract is added; (4) natural gum is added in vegetable tanning agent; (5) add synthetic tanning agent and all can reduce Free-formaldehyde in Leather content.The effect that the document reports organic and inorganic formaldehyde scavenger is all better, but does not report the concrete material of inorganic, organic formaldehyde scavenging agent used.
Zhou Yongxiang is in " development of multi-functional free formaldehyde trapping agent " (Shaanxi: Shaanxi Tech Univ, 2006) systematically have studied in 14 and contain amine (ammonium) micromolecular compound to the elimination effect of leather free formaldehyde, result shows: ammonium acetate, ammonium sulfate, trimeric cyanamide, urea, DMF have good methanal trapping effect.If small molecules formaldehyde scavenger can not be combined with collagen, then easily washed out in subsequent handling; If small molecules formaldehyde scavenger is combined by the group of active group in leather, on its molecule, active function groups reduces, then will greatly can reduce with the active group ratio of formaldehyde reaction, thus effectively can not catch the formaldehyde that leatherware in use discharges, therefore small molecules scavenging agent also has some limitations.
3. macromole free formaldehyde trapping agent
Pass through Molecular Structure Design, synthesize a kind of high polymer containing multiple amino, this polymerization can easily penetrate in leather, and be combined on leather collagen, not easily by water elution, then with this polymer treatment leather, make it to be filled in dermatotome, to catch the formaldehyde that dermatotome constantly discharges, give leather retanning fillibility and assistant dying, should be able to be the effective ways solving leather free formaldehyde problem simultaneously.
At present, the macromole leather free formaldehyde trapping agent research of domestic expansion can be summarized as follows:
(1) Zhou Yongxiang, Cheng Fengxia, old waiting quietly is containing " synthesis of amino polymer free formaldehyde trapping agent " (Chinese leather, 2006,35 (11): 27-33) in, by acrylamide and vinylbenzene are carried out emulsifier-free emulsion polymerization, synthesize acrylamide-St multipolymer, again by amide group through Hoffman DeR, change primary amine groups into, finally obtain the linear copolymer containing polyamino.This product is 30% to the capture rate of fur Free-formaldehyde, has retanning filling and assistant dying energy simultaneously.
(2) Qiang Xihuai, Tian Ling, old state equality is at " research of Amino End Group PAMAM Capturing Ability of Free-formaldehyde in Leather ability " (Chinese leather, 2007,36 (9): 22-24) propose in: with quadrol and methyl acrylate for monomer, adopt divergent method synthesized peripheral be respectively 4 and 8 amino two generation polymeric amide-amine type branch-shape polymer, the application result of this product shows, when the add-on of trapping agent is 2%, the formaldehyde content in leather can be made to reduce about 50%.
(3) Ren Longfang is in " preparation of methanal trapping agent and the research of capturing behavior thereof based on discarded collagen modification " (Shaanxi: Shaanxi Tech Univ, 2006) propose in: with quadrol and diethylenetriamine, graft modification is carried out to gelatin hydrolysate respectively, make the carboxyl amination in gelatin hydrolysate, enhance the response capacity of gelatin hydrolysate PARA FORMALDEHYDE PRILLS(91,95).
In sum, no matter be the method for adding de-aldehyde agent, or strengthen the processing method of mechanical effect, all have some limitations, namely completely for existence form and the free formaldehyde releasing rule of formaldehyde in fur goods, generation and removing two aspects of taking into account free formaldehyde can not be accomplished simultaneously.
Therefore, for the existence form of formaldehyde in fur and goods thereof, the generation characteristic of free formaldehyde and free formaldehyde releasing rule, develop a kind of fur free formaldehyde control of multipath coupling, the existing fur manufacturing eliminated, have the fur manufacturing technique tool of the solid aldehyde effect of aldehydes removal to be of great significance, for a megatrend of free formaldehyde excessive problem after also will being again.
Summary of the invention
The object of the present invention is to provide a kind of method reducing fur Free-formaldehyde content, significantly can reduce fur and goods Free-formaldehyde content thereof and do not cause fur to fade, in the short period of time, fur Free-formaldehyde content can not significantly rebound.
For achieving the above object, the present invention mainly adopts following technical scheme:
Reduce a method for fur Free-formaldehyde content, comprise the steps:
1) get fur to weigh, measure fur Free-formaldehyde content;
2) retanning aldehydes removal
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 40g/L Industrial Salt and 0.4-0.5g/L formic acid are added to the water, put into fur, add 5-8g/L tschermigite and 10-15g/L chrome tanning agent, after 3-4 hour, add 2-3g/L soda ash, regulate pH to 3.8-4.0, retanning is carried out to fur, remove the free formaldehyde in fur, the retanning time is 10-15 hour;
3) free formaldehyde of removing is caught
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, by 4-6g/L Sodium Pyrosulfite, 0.1-0.5g/L clorox, 3-5g/L ammonium sulfate is added to the water, and draws even, put into through step 2) fur that processes, paddling 90-120min, goes out skin control water;
4) washing removes free formaldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 0.5-1.0g/L sodium lauryl sulphate or sodium laurylsulfonate are added to the water, draw even, put into the fur through step 3) process, paddling 30-60min, go out skin control water;
5) solid aldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, normal temperature, 0.1-0.4g/L sodium bicarbonate and 0.1-0.4g/L sodium formiate are added to the water, draw even, put into the fur through step 4) process, add 1.5-3g/L formaldehyde scavenger, paddling 20-30min is 3.6-4.0 to pH value, goes out skin control water, water dumping, dry, arrangement.
Separately, as fur needs dyeing, fixation, then remove between free formaldehyde step and solid aldehyde step in washing and add dye fixation step, the present invention mainly adopts following technical scheme:
Reduce a method for fur Free-formaldehyde content, comprise the steps:
1) get fur to weigh, measure fur Free-formaldehyde content;
2) retanning aldehydes removal
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 40g/L Industrial Salt and 0.4-0.5g/L formic acid are added to the water, put into fur, add 5-8g/L tschermigite and 10-15g/L chrome tanning agent, after 3-4 hour, add 2-3g/L soda ash, regulate pH to 3.8-4.0, retanning is carried out to fur, remove the free formaldehyde in fur, the retanning time is 10-15 hour;
3) removing free formaldehyde is caught
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, by 4-6g/L Sodium Pyrosulfite, 0.1-0.5g/L clorox, 3-5g/L ammonium sulfate is added to the water, and draws even, put into through step 2) fur that processes, paddling 90-120min, goes out skin control water;
4) washing removes free formaldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 0.5-1.0g/L sodium lauryl sulphate or sodium laurylsulfonate are added to the water, draw even, put into the fur through step 3) process, paddling 30-60min, go out skin control water;
5) dye fixing
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 60-65 DEG C, 0.5-1.0g/L levelling agent and 5-10g/L Sodium sulfate anhydrous.min(99) are added to the water, draw even, put into the fur through step 4) process, add xg/L dyestuff, add 1.0-1.5g/L formic acid, adjust ph is to 3.2-3.6, and time 100-120min, goes out skin control water;
6) solid aldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, normal temperature, 0.1-0.4g/L sodium bicarbonate and 0.1-0.4g/L sodium formiate are added to the water, draw even, put into the fur through step 5) process, add 1.5-3g/L formaldehyde scavenger, paddling 20-30min is 3.6-4.0 to pH value, goes out skin control water, water dumping, dry, arrangement.
Wherein, step 2) the retanning aldehydes removal shrinkage temperature that terminates rear fur dermatotome is more than 95 DEG C.
Step 2) Adding Way of soda ash is in retanning aldehydes removal: with the water of soda ash amount 10 times, soda ash is dissolved, point to be added to the water for three times, add once every 30min.
In dye fixation step, the Adding Way of formic acid is: diluted by formic acid 10 times of water, parts by weights is two equal portions, first adds a formic acid, after paddling 30-40 minute, adds another part of formic acid.
Separately, the measuring method of fur Free-formaldehyde adopts national Specification method.
Again, retanning aldehydes removal concrete operations technique is with existing retanning process, at this, details are as follows: get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 40g/L Industrial Salt and 0.4-0.5g/L formic acid are added to the water, draw even, hypodermis, paddling 30min, 5-8g/L tschermigite and 10-15g/L chrome tanning agent, paddling 60min.Per hour stroke after 5min, 3-4 hour later, add 2-3g/L soda ash, after paddling 30min, survey pH=3.8-4.0 with pH meter, after pH reaches requirement, paddling 30min, leaves standstill more than 3 hours, is warming up to 38 DEG C, paddling 30min, hold over night, in morning next day, paddling 10min, drags for skin, control liquid.
Again, unit g/L represents the material mass contained in every premium on currency, and each material adds method for determination of amount: determine the weight of water according to fur weight liquor ratio 20:1 in water and step 1), and then determines each material add-on according to the concentration (g/L) of each material.
And, select fur to be fur base in step 1), namely according to industry common processes to rawhide through immersion, wash skin, soak again, fleshing, degreasing, softening, pickling and tanning, stuffing, drying, the fur that obtains after arrangement.
Wherein, chrome tanning agent is selected: the HLS-C of XiongDi Science Co., Ltd, basicity 33%, chromic oxide content about 25%.Formaldehyde scavenger is selected: the potent formaldehyde scavenger of German Tang Pule company RESISTOLFST.Other materials are commercially available prod.
Compared with prior art, beneficial effect of the present invention is:
A) first carry out chrome retanned to containing free formaldehyde fur, in retanning liquid, add tschermigite, improve the effect removing fur Free-formaldehyde; Tai-Ace S 150 in tschermigite has auxiliary tanning effect to fur, and ammonium sulfate can react with free formaldehyde, contributes to the removing of free formaldehyde;
B) adopt catch-method of wash-out-fixing coupling is caught in step except unhaired hide free formaldehyde at free formaldehyde, select Sodium Pyrosulfite and ammonium sulfate, clorox as trapping agent, effectively can catch the free formaldehyde of removal;
C) remove in free formaldehyde step in washing, select sodium lauryl sulphate or sodium laurylsulfonate as eluent, remove free formaldehyde further; Sodium lauryl sulphate or sodium laurylsulfonate are anionic surfactant, have stronger wetting, infiltration, washing function, contribute to the extraction in conjunction with free formaldehyde;
D) fur Free-formaldehyde content can be reduced to below 70mg/KG from about 450mg/KG, even below 20mg/KG by the method, ensure that fur product quality, and in fur, residual free formaldehyde content complies with the national standard requirements simultaneously;
E) owing to using formaldehyde to carry out tanning for reversible reaction to fur, the formaldehyde combined has larger probability to be again discharged in fur, occur for avoiding this type of situation, the present invention in the end increases solid aldehyde step, guarantee that the formaldehyde combined in fur can not be discharged in fur at short notice again, fur product Free-formaldehyde content can not significantly be rebounded in three months;
F) to the fur needing dyeing, after washing removes free formaldehyde step, increase dye fixation step, improve fur aesthetic property, widen fur market outlook.
Embodiment
Below by specific embodiment, the present invention is described further, but embodiment does not limit the scope of the invention.
Embodiment 1
Family's coney retanning, dyeing, aldehydes removal technique
1) family's coney about 50kg, after measured free formaldehyde content 458.93mg/kg.
2) retanning, aldehydes removal
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 35 DEG C, Industrial Salt: (main component sodium-chlor) 40g/L, formic acid: 0.5g/L, tschermigite 5g/L, the chrome powder (HLS-C of XiongDi Science Co., Ltd, basicity 33%, chromic oxide content about 25%): 15g/L.
Operation: after mixing up water temperature and the water yield, add Industrial Salt and formic acid, draw even, hypodermis, paddling 30min, adds tschermigite and chrome tanning agent, paddling 60min.Per hour stroke of 5min later, after 4 hours, adds soda ash: soda ash dissolves by the water of 2-3g/L(soda ash amount 10 times, divide and add for three times, add once every 30min), after drawing 30min, pH=3.8-4.0 is surveyed with pH meter, after pH reaches requirement, paddling 30min, leave standstill more than 3 hours, be warming up to 38 DEG C, paddling 30min, hold over night, morning next day, paddling 10min, drag for skin, by hydraulic control on skin in paddle-tumble.After mensuration retanning, the shrinkage temperature of dermatotome, reaches 96 DEG C-100 DEG C.
3) aldehydes removal is caught
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 32 DEG C, Sodium Pyrosulfite: 6g/L, clorox: 0.3g/L, ammonium sulfate: 5g/L.
Operation: after mixing up water temperature and the water yield, add Sodium Pyrosulfite and ammonium sulfate, clorox, draw even, hypodermis, paddling 120min, goes out skin control water.
4) aldehydes removal is washed
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 34 DEG C, sodium lauryl sulphate 0.5g/L.
Operation: after mixing up water temperature and the water yield, add sodium lauryl sulphate, draws even, hypodermis, paddling 40min.
5) dyeing, fixation
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 65 DEG C, levelling agent 0.6g/L, Sodium sulfate anhydrous.min(99) 5g/L, add light grey dyestuff 0.5g/L, formic acid 1.3g/L
Operation: after mixing up water temperature and the water yield, add levelling agent and Sodium sulfate anhydrous.min(99), draws even, and throw skin, paddling 15 minutes, adds dyestuff, and paddling 40 minutes, adds half formic acid, and paddling 30 minutes adds remaining half formic acid, paddling 30 minutes, and pH3.4 goes out skin control water.
6) solid aldehyde
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), normal temperature, sodium bicarbonate 0.2g/L, sodium formiate 0.2g/L, the potent formaldehyde scavenger 1.5-3g/L of German Tang Pule company RESISTOL FST
Operate: after mixing up water temperature and the water yield, add sodium bicarbonate and sodium formiate, draw even, throw skin, paddling 10 minutes, adds formaldehyde scavenger, paddling 30 minutes, and pH4.5-5.0, goes out skin, control water, water dumping, conveniently technique drying, arrangement.
Detect through enterprise, free formaldehyde content 11.80mg/kg.After product is placed 3 months, measure free formaldehyde content 19mg/kg ,≤20mg/kg.
Quality examination is carried out to the dyeing man coney.
Test basis: QB/T1284-2005 " mensuration of leather and fur chemical test forbidding azo dyes ", GB/T19941-2005 " mensuration of leather and fur chemical test formaldehyde content ", QB/T1270-1991 " mensuration of fur finished product elongation ", QB/T2711-2005 " mensuration of leather physics and mechanical testing tear edge: bilateral tear ", QB/T2725-2005 " mensuration of leather smells ", QB/T2924-2007 " fur perspiration resistance Se Laodu test method ".
Judgment basis: with reference to QB/T1284-2007 " coney "
Interventions Requested: forbidding azo dyes, tear edge, load elongation, smell, fur colour fastness to perspiration, free formaldehyde, shrinkage temperature, moisture and volatile matter content, ash content, pH value, sexavalent chrome, pentachlorophenol.
Detected result is referring to such as following table 2 and table 3.
Table 2
Table 3
Note: in forbidding azo dyes project, measured data " does not detect " and represents measured value≤30mg/kg; Or as 4-phenylaniline, 2-naphthylamines content >30mg/kg, because prior art cannot measure, therefore measured data is also " not detecting ".
And fur Free-formaldehyde content is 19mg/kg after three months.
As can be seen from above-mentioned detected result, through the coney fur product satisfactory quality of the inventive method process, especially free formaldehyde content is much better than standard-required, so this aldehydes removal technique is feasible.
Embodiment 2
The retanning of recoon dog fur, dyeing, aldehydes removal technique
1) recoon dog fur about 50kg, free formaldehyde content 661mg/KG.
2) retanning, aldehydes removal
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 35 DEG C, Industrial Salt: (main component sodium-chlor) 40g/L, formic acid: 0.5g/L, tschermigite 7g/L, the chrome powder (HLS-C of XiongDi Science Co., Ltd, basicity 33%, chromic oxide content about 25%): 13g/L.
Operation: after mixing up water temperature and the water yield, add Industrial Salt and formic acid, draw even, hypodermis, paddling 30min, adds tschermigite and chrome tanning agent, paddling 60min.Per hour stroke of 5min later, after 4 hours, adds soda ash: soda ash dissolves by the water of 3g/L(soda ash amount 10 times, divide and add for three times, add once every 30min), after drawing 30min, pH=3.8-4.0 is surveyed with pH meter, after pH reaches requirement, paddling 30min, leave standstill more than 3 hours, be warming up to 38 DEG C, paddling 30min, hold over night, morning next day, paddling 10min, drag for skin, by hydraulic control on skin in paddle-tumble.After mensuration retanning, the shrinkage temperature of dermatotome, reaches 96 DEG C-100 DEG C.
3) aldehydes removal is caught
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 32 DEG C, Sodium Pyrosulfite: 4g/L, clorox: 0.1g/L, ammonium sulfate: 5g/L.
Operation: after mixing up water temperature and the water yield, add Sodium Pyrosulfite and ammonium sulfate, clorox, draw even, hypodermis, paddling 120min, goes out skin control water.
4) aldehydes removal is washed
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 34 DEG C, sodium laurylsulfonate 0.5g/L.
Operation: after mixing up water temperature and the water yield, add sodium laurylsulfonate, draws even, hypodermis, paddling 40min.
5) dyeing, fixation
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 65 DEG C, levelling agent 0.6g/L, Sodium sulfate anhydrous.min(99) 5g/L, add dyestuff 0.7g/L, formic acid 1.5g/L
Operation: after mixing up water temperature and the water yield, add levelling agent and Sodium sulfate anhydrous.min(99), draws even, and throw skin, paddling 15 minutes, adds dyestuff, and paddling 30 minutes, adds half formic acid, and paddling 30 minutes adds remaining half formic acid, paddling 30 minutes, and pH3.3 goes out skin control water.
6) solid aldehyde
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), normal temperature, sodium bicarbonate 0.2g/L, sodium formiate 0.4g/L, the potent formaldehyde scavenger 2.0g/L of German Tang Pule company RESISTOL FST
Operate: after mixing up water temperature and the water yield, add sodium bicarbonate and sodium formiate, draw even, throw skin, paddling 10 minutes, adds formaldehyde scavenger, paddling 30 minutes, and pH4.0-4.5, goes out skin, control water, water dumping, conveniently technique drying, arrangement.
Free formaldehyde content 25.5mg/kg is detected through enterprise.
Embodiment 3
The retanning of true qualities recoon dog fur, aldehydes removal technique
1) recoon dog fur about 50kg, measures free formaldehyde content 442.11mg/kg through enterprise
2) retanning, aldehydes removal
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 35 DEG C, Industrial Salt: (main component sodium-chlor) 40g/L, formic acid: 0.5g/L, tschermigite 7g/L, the chrome powder (HLS-C of XiongDi Science Co., Ltd, basicity 33%, chromic oxide content 25%): 13g/L.
Operation: after mixing up water temperature and the water yield, add Industrial Salt and formic acid, draw even, hypodermis, paddling 30min, adds tschermigite and chrome tanning agent, paddling 60min.Per hour stroke of 5min later, after 4 hours, adds soda ash: soda ash dissolves by the water of 3g/L(soda ash amount 10 times, divide and add for three times, add once every 30min), after drawing 30min, pH=3.8-4.0 is surveyed with pH meter, after pH reaches requirement, paddling 30min, leave standstill more than 3 hours, be warming up to 38 DEG C, paddling 30min, hold over night, morning next day, paddling 10min, drag for skin, by hydraulic control on skin in paddle-tumble.After mensuration retanning, the shrinkage temperature of dermatotome, reaches 95 DEG C-100 DEG C.
3) aldehydes removal is caught
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 32 DEG C, Sodium Pyrosulfite: 4g/L, clorox: 0.5g/L, ammonium sulfate: 5g/L.
Operation: after mixing up water temperature and the water yield, add Sodium Pyrosulfite and ammonium sulfate, clorox, draw even, hypodermis, paddling 120min, goes out skin control water.
4) aldehydes removal is washed
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), temperature 34 DEG C, sodium lauryl sulphate 0.3g/L.
Operation: after mixing up water temperature and the water yield, add sodium lauryl sulphate, draws even, hypodermis, paddling 40min.
Free formaldehyde content 62.75mg/kg is detected through enterprise.
5) solid aldehyde
Equipment: 1000L paddle-tumble, water and fur liquor ratio: 20(mass ratio), normal temperature, the potent formaldehyde scavenger 2.0g/L of German Tang Pule company RESISTOL FST
Operate: after mixing up water temperature and the water yield, add formaldehyde scavenger, draw even, throw skin, paddling 30 minutes, pH4.5-5.0, goes out skin, control water, water dumping, conveniently technique drying, arrangement.
Detect through enterprise, free formaldehyde content 13.28mg/kg.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (5)
1. reduce a method for fur Free-formaldehyde content, it is characterized in that, comprise the steps:
1) get fur to weigh, measure fur Free-formaldehyde content;
2) retanning aldehydes removal
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 40g/L Industrial Salt and 0.4-0.5g/L formic acid are added to the water, put into fur, add 5-8g/L tschermigite and 10-15g/L chrome tanning agent, after 3-4 hour, add 2-3g/L soda ash, regulate pH to 3.8-4.0, retanning is carried out to fur, remove the free formaldehyde in fur, the retanning time is 10-15 hour;
3) removing free formaldehyde is caught
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, by 4-6g/L Sodium Pyrosulfite, 0.1-0.5g/L clorox, 3-5g/L ammonium sulfate is added to the water, and draws even, put into through step 2) fur that processes, paddling 90-120min, goes out skin control water;
4) washing removes free formaldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 0.5-1.0g/L sodium lauryl sulphate or sodium laurylsulfonate are added to the water, draw even, put into the fur through step 3) process, paddling 30-60min, go out skin control water;
5) solid aldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, normal temperature, 0.1-0.4g/L sodium bicarbonate and 0.1-0.4g/L sodium formiate are added to the water, draw even, put into the fur through step 4) process, add 1.5-3g/L formaldehyde scavenger, paddling 20-30min is 3.6-4.0 to pH value, goes out skin control water, water dumping, dry, arrangement.
2. reduce a method for fur Free-formaldehyde content, it is characterized in that, comprise the steps:
1) get fur to weigh, measure fur Free-formaldehyde content;
2) retanning aldehydes removal
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 40g/L Industrial Salt and 0.4-0.5g/L formic acid are added to the water, put into fur, add 5-8g/L tschermigite and 10-15g/L chrome tanning agent, after 3-4 hour, add 2-3g/L and regulate pH to 3.8-4.0, carry out retanning to fur, remove the free formaldehyde in fur, the retanning time is 10-15 hour;
3) free formaldehyde of removing is caught
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, by 4-6g/L Sodium Pyrosulfite, 0.1-0.5g/L clorox, 3-5g/L ammonium sulfate is added to the water, and draws even, put into through step 2) fur that processes, paddling 90-120min, goes out skin control water;
4) washing removes free formaldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 32-35 DEG C, 0.5-1.0g/L sodium lauryl sulphate or sodium laurylsulfonate are added to the water, draw even, put into the fur through step 3) process, paddling 30-60min, go out skin control water; 5) dye fixing
Get and the water of pelage quality in step 1) than the amount for 20:1, regulate water temperature to 60-65 DEG C, 0.5-1.0g/L levelling agent and 5-10g/L Sodium sulfate anhydrous.min(99) are added to the water, draw even, put into the fur through step 4) process, add 0.5-3.0g/L dyestuff, add 1.0-1.5g/L formic acid, adjust ph is to 3.2-3.6, and time 100-120min, goes out skin control water;
6) solid aldehyde
Get and the water of pelage quality in step 1) than the amount for 20:1, normal temperature, 0.1-0.4g/L sodium bicarbonate and 0.1-0.4g/L sodium formiate are added to the water, draw even, put into the fur through step 5) process, add 1.5-3g/L formaldehyde scavenger, paddling 20-30min is 3.6-4.0 to pH value, goes out skin control water, water dumping, dry, arrangement.
3. a kind of method reducing fur Free-formaldehyde content according to claim 1 and 2, is characterized in that, step 2) the retanning aldehydes removal shrinkage temperature that terminates rear fur dermatotome is more than 95 DEG C.
4. a kind of method reducing fur Free-formaldehyde content according to claim 1 and 2, it is characterized in that, step 2) Adding Way of soda ash is in retanning aldehydes removal: with the water of soda ash amount 10 times, soda ash is dissolved, point to be added to the water for three times, add once every 30min.
5. a kind of method reducing fur Free-formaldehyde content according to claim 2, it is characterized in that, in dye fixation step, the Adding Way of formic acid is: diluted by formic acid 10 times of water, parts by weights is two equal portions, first add a formic acid, after paddling 30-40 minute, add another part of formic acid.
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| CN201310703427.3A CN104726621A (en) | 2013-12-19 | 2013-12-19 | Fur free formaldehyde content reducing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107217518A (en) * | 2017-07-24 | 2017-09-29 | 北京泛博化学股份有限公司 | A kind of firm elevator of perspiration resistance and preparation method thereof, application |
| CN110791948A (en) * | 2019-11-01 | 2020-02-14 | 赤壁祥源特种布有限公司 | Formaldehyde removal process for textiles |
| CN113293241A (en) * | 2021-06-01 | 2021-08-24 | 嘉兴学院 | Method for treating free formaldehyde in fur product |
| CN114540558A (en) * | 2021-12-14 | 2022-05-27 | 浙江中辉裘革科技有限公司 | Method for removing free formaldehyde from fur by combined capturing, eluting and fixing |
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2013
- 2013-12-19 CN CN201310703427.3A patent/CN104726621A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107217518A (en) * | 2017-07-24 | 2017-09-29 | 北京泛博化学股份有限公司 | A kind of firm elevator of perspiration resistance and preparation method thereof, application |
| CN107217518B (en) * | 2017-07-24 | 2019-06-07 | 北京泛博化学股份有限公司 | A kind of secured elevator of perspiration resistance and preparation method thereof, application |
| CN110791948A (en) * | 2019-11-01 | 2020-02-14 | 赤壁祥源特种布有限公司 | Formaldehyde removal process for textiles |
| CN113293241A (en) * | 2021-06-01 | 2021-08-24 | 嘉兴学院 | Method for treating free formaldehyde in fur product |
| CN114540558A (en) * | 2021-12-14 | 2022-05-27 | 浙江中辉裘革科技有限公司 | Method for removing free formaldehyde from fur by combined capturing, eluting and fixing |
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Application publication date: 20150624 |