CN114540558A - Method for removing free formaldehyde from fur by combined capturing, eluting and fixing - Google Patents
Method for removing free formaldehyde from fur by combined capturing, eluting and fixing Download PDFInfo
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- CN114540558A CN114540558A CN202111537297.1A CN202111537297A CN114540558A CN 114540558 A CN114540558 A CN 114540558A CN 202111537297 A CN202111537297 A CN 202111537297A CN 114540558 A CN114540558 A CN 114540558A
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- water
- scratching
- fur
- cutting
- groove
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Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 492
- 238000000034 method Methods 0.000 title claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 279
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 69
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000004043 dyeing Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims description 169
- 238000006748 scratching Methods 0.000 claims description 162
- 230000002393 scratching effect Effects 0.000 claims description 162
- 239000007788 liquid Substances 0.000 claims description 147
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 104
- 239000002994 raw material Substances 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 56
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 54
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 52
- 235000019253 formic acid Nutrition 0.000 claims description 52
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 35
- 239000002516 radical scavenger Substances 0.000 claims description 33
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 32
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 32
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 claims description 28
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 28
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 27
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 27
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 26
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 26
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 26
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 20
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 18
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 18
- 239000004280 Sodium formate Substances 0.000 claims description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 16
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 16
- 235000019254 sodium formate Nutrition 0.000 claims description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010985 leather Substances 0.000 description 47
- 239000000047 product Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000000975 dye Substances 0.000 description 12
- 241000282330 Procyon lotor Species 0.000 description 11
- 239000000987 azo dye Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 241000283973 Oryctolagus cuniculus Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000003389 potentiating effect Effects 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000002146 bilateral effect Effects 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007705 chemical test Methods 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 241000219312 Chenopodium Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- KMNONFBDPKFXOA-UHFFFAOYSA-N prop-2-enamide;styrene Chemical compound NC(=O)C=C.C=CC1=CC=CC=C1 KMNONFBDPKFXOA-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- -1 small molecule compounds Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 210000000051 wattle Anatomy 0.000 description 1
Classifications
-
- 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
- C14C3/06—Mineral tanning using chromium compounds
-
- 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
-
- 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/653—Nitrogen-free carboxylic acids or their salts
- D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
-
- 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
Abstract
The invention relates to a fur production process, in particular to a method for removing and fixing free formaldehyde in fur, which is characterized in that the fur containing free formaldehyde and needing aldehyde removal is weighed, and the content of the free formaldehyde is measured and is used as the basis of water and chemical material usage amount in the following operation procedures; 2) retanning and removing aldehyde; 3) capturing and removing aldehyde; 4) washing to remove aldehyde; 5) dyeing and fixing color; 6) aldehyde fixation; and finally obtaining the fur with the free formaldehyde removed, wherein the method can reduce the content of the free formaldehyde in the fur from about 450mg/KG to below 70mg/KG, even below 20mg/KG, and combines the formaldehyde removal with the fur retanning and dyeing processes to ensure the quality of the fur product, and meanwhile, the content of the free formaldehyde meets the national standard requirement, and the content of the free formaldehyde in the fur product can not rebound within three months.
Description
Technical Field
The invention relates to a fur production process, in particular to a method for removing and fixing free formaldehyde in fur.
Background
With the increasing awareness of green consumption of domestic and foreign consumers, large buyers who import leather from developing countries often attach limit regulations of specific chemical substances in leather in order to avoid the danger of compensation due to possible negative effects of the chemical substances in the leather products on human bodies, the situation that export products encounter technical trade barriers in the importing countries is rare. This trend has constituted a technical trade barrier affecting the entry of leather and leather products into the international market in our country. These technical trade barriers exist in the form of european union directives or standards self-imposed by certain countries.
Free formaldehyde is one of the chemicals that may be harmful to the human body in the leather targeted by the technical trade barrier. The problem of free formaldehyde content has attracted more national attention, and many countries adopt strict limits on the formaldehyde content in leather and products thereof, and the limit standards of free formaldehyde in partial products are shown in table 1.
On the other hand, formaldehyde has to be used in large amounts in many cases because of its outstanding cost-effectiveness. Taking leather processing as an example, tanning is the core of leather processing, and is a processing process for turning the chemical properties of a product through the chemical reaction of a chemical reagent and skin protein. The materials (tanning agents) which can produce tanning effect on leather protein and can be industrially used at present mainly comprise chrome tanning agents (chrome complex), vegetable tannins and aldehyde tanning agents. The chrome tanning agent has the best comprehensive effect on tanning, but the shortage of chrome resources causes serious environmental pollution, and less chrome tanning and chrome-free tanning are urgent. The comprehensive effect of the formaldehyde tanning in all tanning agents is inferior to that of chrome tanning, and the formaldehyde is cheap and easy to obtain, convenient to use and low in tanning cost, and particularly, the formaldehyde tanned leather is superior to chrome tanning in the aspects of water washing resistance, sweat resistance, oxidant resistance, reducing agent resistance and the like, so that the formaldehyde is widely applied to tanning of fur and used as a monomer of a synthetic tanning agent.
Formaldehyde is an indispensable raw material for processing products such as adhesives, coatings, interior decoration materials, fiber boards and the like. The limited amount of free formaldehyde in products and the unique application performance and irreplaceability of formaldehyde in various countries around the world form a plurality of green barriers and technical barriers in international trade.
Current research situation and development trend at home and abroad
Studies have shown that four types of binding of formaldehyde to proteins in the skin and their respective characteristics are as follows: 1, physical adsorption, easy to wash off by water; o2 is in dynamic chemical equilibrium and can be changed by the medium; o3 stable binding, but chemically reversible, can be acted upon by chemical agents to reduce binding; o4 stable and chemically irreversible covalent bonding, resistance to acid, base, chemical agents. The formaldehyde in the state of physical adsorption and dynamic chemical equilibrium is the largest formaldehyde source, and the release of the free formaldehyde in the fur product has long-term and slow-going property from various combined morphological analyses of the formaldehyde and protein.
At present, the existing reports on the mature methods for solving the problem of free formaldehyde in leather and fur products are few, and the method mainly focuses on adding inorganic and organic compounds capable of reacting with formaldehyde; process improvement methods and the like.
1. Improve leather production process, reduce free formaldehyde content in leather and leather making process
Liu Jian proposed: (1) adjusting mechanical operations such as water washing operation and drying operation; (2) enhancing mechanical operations such as intensive water washing, high drying temperatures, increased drum capacity or increased rotational speed, etc., helps to reduce the free formaldehyde content of the product.
2. Scavenging or reducing free formaldehyde with small molecule free formaldehyde scavenger
The following methods are proposed: (1) adding an organic formaldehyde scavenger; (2) adding an inorganic formaldehyde scavenger; (3) adding wattle bark tannin extract; (4) adding gum into vegetable tanning agent; (5) the free formaldehyde content in the leather can be reduced by adding the synthetic tanning agent. The document reports that both organic and inorganic formaldehyde scavengers have good effects, but specific substances of the used inorganic and organic formaldehyde scavengers are not reported.
The scavenging effect of fourteen small molecule compounds containing amine (ammonium) on free formaldehyde of leather is systematically studied by Zhouyingxiang and Chengfeng knight, and the results show that: ammonium acetate, ammonium sulfate, melamine, urea and N, N-dimethylformamide have a good formaldehyde capture effect. If the micromolecular formaldehyde scavenger can not be combined with the collagen, the micromolecular formaldehyde scavenger is easy to be washed out by water in the subsequent process; if the micromolecular formaldehyde scavenger is combined with the groups in the leather through the active groups, and the active functional groups on the molecules are reduced, the proportion of the active groups capable of reacting with formaldehyde is greatly reduced, so that the formaldehyde released in the use process of the leather product cannot be effectively captured, and therefore, the micromolecular formaldehyde scavenger also has certain limitation.
3 macromolecular free formaldehyde trapping agent
Through molecular structure design, a macromolecular polymer containing a plurality of amino groups is synthesized, the polymer can easily permeate into leather, is combined on leather collagen and is not easy to be eluted by water, and the polymer is used for treating the leather to fill in a leather board so as to capture formaldehyde continuously released by the leather board and endow retanning filling property and dyeing assisting property to the leather, which is an effective method for solving the problem of free formaldehyde of the leather.
At present, the research on the macromolecular leather free formaldehyde trapping agent developed in China can be summarized as follows:
(1) zhouyangxiang, chenopodium amboinense and the like synthesize acrylamide-styrene binary copolymer by soap-free emulsion polymerization of acrylamide and styrene, and then the amide groups are converted into primary amine groups by Hoffman degradation reaction, and finally the linear copolymer containing multiple amino groups is obtained. The product has a capture rate of 30% for free formaldehyde in fur, and has retanning, filling and dyeing assisting performances.
(2) The application result of the product shows that when the addition amount of the trapping agent is 2%, the formaldehyde content in the leather can be reduced by about 50%.
(3) The hydrolyzed gelatin is grafted and modified by ethylenediamine and diethylenetriamine to make the carboxyl in the hydrolyzed gelatin aminated and enhance the reaction capacity of the hydrolyzed gelatin to formaldehyde.
Both the method of adding the formaldehyde removing agent and the process method of enhancing the mechanical action have certain limitations, namely the method can not completely aim at the existence form and the release rule of the formaldehyde in the fur products, and simultaneously can give consideration to the two aspects of generating and removing the free formaldehyde. Therefore, aiming at the existence form of formaldehyde in the fur and products thereof, the generation characteristic of free formaldehyde and the release rule of the free formaldehyde, the development of a fur processing technology which has the effects of preventing and eliminating the free formaldehyde of the fur through combination of multiple ways and has the effects of removing the formaldehyde and fixing the formaldehyde has very important significance, and the technology is a major trend for solving the problem that the free formaldehyde exceeds the standard.
Disclosure of Invention
The invention aims to provide a method which can obviously reduce the content of free formaldehyde in fur and products thereof, does not cause the fur to fade and does not rebound the content of the free formaldehyde in a short time. The method can reduce the content of free formaldehyde in the fur from about 450mg/KG to below 70mg/KG, even below 20mg/KG, and combines the formaldehyde removal with the fur retanning and dyeing process, thereby ensuring the quality of the fur product, and meanwhile, the content of the free formaldehyde meets the national standard requirement, and the content of the free formaldehyde in the fur product can not rebound within three months.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing free formaldehyde from fur by using capture-elution-fixation combination is characterized by comprising the following steps:
the method comprises the following steps:
1) weighing the fur containing free formaldehyde and needing to remove the aldehyde, and measuring the content of the free formaldehyde to be used as the basis of the water and chemical material usage amount in the following operation procedures;
2) retanning and removing aldehyde;
3) capturing and removing aldehyde;
4) washing to remove aldehyde;
5) dyeing and fixing color;
6) aldehyde fixation;
finally obtaining the fur with the free formaldehyde removed.
Preferably, the specific operation steps of retanning and aldehyde removal are as follows:
equipment: scratching a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 32-35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: 30-40g/L, formic acid: 0.4-0.5g/L, 5-8g/L of ammonium alum, powdery chrome tanning agent: 10-15 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 h, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing out the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and requiring to reach more than 95 ℃.
Preferably, the operation steps of trapping and removing aldehyde are as follows:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32-35 ℃, and the fur liquid B is prepared from the following raw materials in parts by weight: sodium metabisulfite: 4-6g/L, sodium hypochlorite: 0.1-0.5g/L, ammonium sulfate: 3-5 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, sodium pyrosulfite and ammonium sulfate are added into a groove of the equipment, the equipment is used for uniformly scratching, peeling is carried out, the equipment is used for scratching for 90-120min, the water is controlled after peeling, and the water is drained and drained.
Preferably, the washing and aldehyde removing operation steps are as follows:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 32-35 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.1-0.2 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate into a groove of the equipment, uniformly scratching, peeling, scratching for 30-60min, discharging the skin, controlling water, and draining the water.
Preferably, the dyeing and fixing operation steps are as follows:
equipment: scratching a groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 60-65 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 0.5-1.0g/L of leveling agent, 5-10g/L of anhydrous sodium sulphate, 0.5-2 g/L of dye and 1.0-1.5g/L of formic acid;
the operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 10-15min, adding a dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after skin emergence, and draining the water after cutting.
Preferably, the aldehyde fixing operation steps are as follows:
equipment: scratching a groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: 0.1-0.4g/L of baking soda, 0.1-0.4g/L of sodium formate and 1.5-3g/L of formaldehyde scavenger;
the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is scratched evenly, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 20-30min, the pH value is 3.6-5.0, the skin is taken out, the water is controlled, the water is thrown, and the drying and the finishing are carried out according to the conventional process.
A method for removing free formaldehyde from fur through capture-elution-fixation combination is characterized by comprising the following steps:
1) weighing the fur containing free formaldehyde and needing to remove the aldehyde, and measuring the content of the free formaldehyde to be used as the basis of the water and chemical material usage amount in the following operation procedures;
2) retanning and removing aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 35 ℃, and the fur liquid A is prepared from the following raw materials in parts by weight: industrial salt: 40g/L, formic acid: 0.5g/L, 7g/L of ammonium alum, powdery chrome tanning agent: 13 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing out the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and requiring to reach more than 95 ℃;
3) capturing and removing aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32 ℃, and the fur liquid B is prepared from the following raw materials in parts by weight: sodium metabisulfite: 4g/L, ammonium sulfate: 4 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium pyrosulfite and ammonium sulfate on a cutting groove of equipment, uniformly cutting, peeling, cutting for 90-120min, discharging the peel, controlling water, and draining the water;
4) washing to remove aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 34 ℃, and the fur liquid C is prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.3 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30-60min, discharging the peel, controlling water, and draining the liquid in the cutting groove;
5) dyeing and fixing color:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 65 ℃, and the fur liquid D is prepared from the following raw materials in parts by weight: 1.0g/L of leveling agent, 8g/L of anhydrous sodium sulphate, 0.7g/L of dye and 1.5g/L of formic acid;
the operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 10-15min, adding a dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after skin discharge, and draining the water after cutting;
6) aldehyde fixation
Equipment: cutting a groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is prepared from the following raw materials in parts by weight at normal temperature: 0.2g/L of baking soda, 0.4g/L of sodium formate and 2g/L of formaldehyde scavenger;
the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is scratched evenly, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 20-30min, the pH value is 3.6-5.0, the skin is taken out, the water is controlled, the water is thrown, and the drying and the finishing are carried out according to the conventional process.
A method for removing free formaldehyde from fur through capture-elution-fixation combination is characterized by comprising the following steps:
1) weighing the fur containing free formaldehyde and needing to remove the aldehyde, and measuring the content of the free formaldehyde to be used as the basis of the water and chemical material usage amount in the following operation procedures;
2) retanning and removing aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 32-35 ℃, and the fur liquid A is prepared from the following raw materials in parts by weight: industrial salt: 30-40g/L, formic acid: 0.4-0.5g/L, 5-8g/L of ammonium alum, powdery chrome tanning agent: 10-15 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing out the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and requiring to reach more than 95 ℃;
3) capturing and removing aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32-35 ℃, and the fur liquid B is prepared from the following raw materials in parts by weight: sodium metabisulfite: 4-6g/L, sodium hypochlorite: 0.1-0.5g/L, ammonium sulfate: 3-5 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite into a cutting groove of equipment, uniformly cutting, peeling, cutting for 90-120min, and discharging and controlling water;
4) washing to remove aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 32-35 ℃, and the fur liquid C is prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.1-0.2 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding sodium dodecyl sulfate into a scratch groove of the equipment, scratching uniformly, peeling, and scratching for 30-60 min;
5) aldehyde fixation
Equipment: cutting a groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is prepared from the following raw materials in parts by weight at normal temperature: 2.0g/L of formaldehyde scavenger;
the operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, adding a formaldehyde scavenger, uniformly scratching, throwing the leather, scratching for 30min, controlling water, throwing the water, drying and finishing according to a conventional process, wherein the pH value is 4.5-5.0, and the leather is taken out.
Preferably, the volume of the scribing groove is 500-1000L.
Compared with the prior art, the invention has the following beneficial effects: the method can reduce the content of free formaldehyde in the fur from about 450mg/KG to below 70mg/KG, even below 20mg/KG, and combines the formaldehyde removal with the fur retanning and dyeing process, thereby ensuring the quality of the fur product, and meanwhile, the content of the free formaldehyde meets the national standard requirement, and the content of the free formaldehyde in the fur product can not rebound within three months.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
Example 1A method for removing free formaldehyde from fur by combined capturing-eluting-fixing process applied to retanning, dyeing and removing formaldehyde from rabbit fur
1) 50kg of rabbit fur, and the content of free formaldehyde is determined to be 458.93 mg/kg;
2) retanning and removing aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 40g/L, formic acid: 0.5g/L, 5g/L of ammonium alum and 15g/L of powdery chrome tanning agent.
The operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, adding ammonium alum and chrome tanning agent, and cutting for 60 min. After 5min of hourly stroke, 4 hours later, soda ash is added: 3g/L (dissolving soda by using water with 10 times of the amount of soda, adding the soda by three times, adding the soda once every 30 min), scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for 30min, standing overnight, scratching for 10min in the next morning, picking out the skin, controlling the skin upper liquid into a scratching groove, determining the shrinkage temperature of a retanned skin plate to reach 96 ℃, draining the liquid by scratching the groove;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 6g/L, sodium hypochlorite: 0.3g/L, ammonium sulfate: 5 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite on a cutting groove of equipment, uniformly cutting, peeling, cutting for 120min, discharging skin, controlling water, and draining the water;
3) washing to remove aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 32 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.2 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding the sodium dodecyl sulfate into a groove of the equipment, uniformly scratching, peeling and scratching for 40 min.
4) Dyeing and fixing color
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 65 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 0.6g/L of leveling agent, 5g/L of anhydrous sodium sulphate, 0.5g/L of light gray dye and 1.3g/L of formic acid
The operation is as follows: after the water temperature and the water quantity are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 15min, adding a dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after the skin is discharged, and draining the water in the cutting groove;
5) aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: sodium bicarbonate 0.2g/L, sodium formate 0.2g/L, RESISTOL FST potent formaldehyde scavenger 3g/L
The operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is evenly scratched, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 30min, the pH value is 5.0, the skin is taken out, the water is controlled, the water is thrown away, and the drying and the finishing are carried out according to the conventional process.
Through enterprise detection, the content of free formaldehyde is reduced from 458.93mg/kg to 11.80 mg/kg.
Example 2 a method for removing free formaldehyde from fur by combined capturing-eluting-fixing process applied to retanning, dyeing and removing formaldehyde from rabbit fur
1) 50kg of rabbit fur, and the content of free formaldehyde is determined to be 456.88 mg/kg;
2) retanning and removing aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 32 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 30g/L, formic acid: 0.4g/L, 8g/L of ammonium alum and 10g/L of powdery chrome tanning agent.
The operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, adding ammonium alum and chrome tanning agent, and cutting for 60 min. After 5min of hourly stroke, 4 hours later, soda ash is added: 3g/L (dissolving soda by using water with 10 times of the amount of soda, adding the soda by three times, adding the soda once every 30 min), scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for 30min, standing overnight, scratching for 10min in the next morning, picking out the skin, controlling the skin upper liquid into a scratching groove, determining the shrinkage temperature of the retanning skin plate, reaching 98 ℃, and draining the liquid by scratching the groove;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 35 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 4g/L, sodium hypochlorite: 0.1g/L, ammonium sulfate: 3 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite on a cutting groove of equipment, uniformly cutting, peeling, cutting for 90min, discharging skin, controlling water, and draining the water;
3) washing to remove aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 35 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.1 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, draining and discharging water;
4) dyeing and fixing color
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 60 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 0.5g/L of leveling agent, 10g/L of anhydrous sodium sulphate, 2g/L of light gray dye and 1.5g/L of formic acid
The operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 10min, adding 2g/L of dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after skin discharging, and draining the water after cutting;
5) aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: sodium bicarbonate 0.1g/L, sodium formate 0.1g/L, RESISTOL FST potent formaldehyde scavenger 1.5g/L of Germany Thompler company;
the operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is evenly scratched, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 20min, the pH value is 3.6, the skin is taken out, the water is controlled, the water is thrown away, and the drying and the finishing are carried out according to the conventional process.
Through enterprise detection, the content of free formaldehyde is reduced from 456.88mg/kg to 10.50 mg/kg.
Example 3 implementation of a trapping-elution-fixation combined method for removing free formaldehyde from fur
1) 50kg of rabbit fur, and the content of free formaldehyde is determined to be 458.66 mg/kg;
2) retanning and removing aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 34 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 35g/L, formic acid: 0.45g/L, 6g/L of ammonium alum and 12/L of powdery chrome tanning agent.
The operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, adding ammonium alum and chrome tanning agent, and cutting for 60 min. After 5min every hour, 4 hours later, soda ash was added: 3g/L (dissolving soda by using water with 10 times of the amount of soda, adding the soda by three times, adding the soda once every 30 min), scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for 30min, standing overnight, scratching for 10min in the next morning, picking out the skin, controlling the skin upper liquid into a scratching groove, determining the shrinkage temperature of the retanning skin plate, reaching 100 ℃, and draining the liquid by scratching the groove;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 34 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 5g/L, sodium hypochlorite: 0.5g/L, ammonium sulfate: 4 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite on a cutting groove of equipment, uniformly cutting, peeling, cutting for 100min, discharging skin, controlling water, and draining the water;
3) washing to remove aldehyde
Equipment: cutting into 1000L slots, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 33 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.15 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 60min, and draining the water and the liquor in the cutting groove;
4) dyeing and fixing color
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 62 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 1.0g/L of leveling agent, 8g/L of anhydrous sodium sulphate, 2g/L of light gray dye and 1.0g/L of formic acid
The operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 12min, adding 2g/L of dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after skin discharging, and draining the water after cutting;
5) aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: sodium bicarbonate 0.4g/L, sodium formate 0.4g/L, RESISTOL FST potent formaldehyde scavenger 2g/L of Thompler Germany
The operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is evenly scratched, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 25min, the pH value is 4.5, the skin is taken out, the water is controlled, the water is thrown away, and the drying and the finishing are carried out according to the conventional process.
Through enterprise detection, the content of free formaldehyde is reduced from 458.66mg/kg to 11.20 mg/kg.
The quality of the rabbit fur dyed by the test center of the research institute of fur and shoe industry in Jiaxing city is tested.
The inspection basis is as follows: QB/T1284 & 2005 & lt & ltdetermination of azo dyes forbidden in leather and fur chemistry test & gt, GB/T19941-2005 & lt & gt determination of formaldehyde content in leather and fur chemistry test & lt & gt, QB/T1270 & lt 1991 & gt determination of elongation of finished fur & lt & gt, QB/T2711 & lt & gt 2005 & lt & gt determination of tearing force in leather physical and mechanical tests & lt: bilateral tear, QB/T2725-.
The judgment basis is as follows: refer to QB/T1284-2007 Rabbit fur
And (4) checking items: disablement of azo dyes, tear strength, elongation under load, odor, fastness of the skins to perspiration, free formaldehyde, shrinkage temperature, moisture and volatiles, ash, pH, hexavalent chromium, pentachlorophenol.
The test results are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
Note: the practical measurement data of 'not detected' in the forbidden azo dye project represents that the practical measurement value is less than or equal to 30 mg/kg; or when the content of the 4-aminobiphenyl and the 2-naphthylamine is more than 30mg/kg, the prior art can not determine, so the data is 'undetected'.
The detection results show that the quality of the rabbit fur products treated by the method meets the requirements, and particularly, the content of free formaldehyde is far superior to the standard requirement, so that the formaldehyde removal process is feasible.
Example 4 a method for removing free formaldehyde from fur by combined capturing, eluting and fixing, which is applied to the processes of retanning, dyeing and removing formaldehyde from racoon dog fur
1) 50kg of raccoon fur;
2) retanning and removing aldehyde
Equipment: cutting into 1000L slots, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 40g/L, formic acid: 0.5g/L, 7g/L of ammonium alum, and powdery chrome tanning agent (HLS-C of Brother science and technology Co., Ltd., basicity 33%, chromic oxide content 25%): 13 g/L.
The operation is as follows: after the water temperature and water amount are adjusted, adding industrial salt and formic acid, uniformly scratching, peeling, scratching for 30min, adding ammonium alum and chrome tanning agent, and scratching for 60 min. After 5min of hourly stroke, 4 hours later, soda ash is added: 3g/L (dissolving soda with water 10 times of soda amount, adding in three times, adding every 30 min), scratching for 30min, measuring pH with pH 3.8-4.0, scratching for 30min after pH meets the requirement, standing for more than 3 hr, heating to 38 deg.C, scratching for 30min, standing overnight, scratching for 10min the next morning, picking skin, and controlling the skin upper liquid to scratch the tank. Measuring the shrinkage temperature of the retanned leather board to 96 ℃, and grooving, draining water and draining liquid;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 4g/L, ammonium sulfate: 5 g/L.
The operation is as follows: after the water temperature and the water amount are adjusted, adding sodium metabisulfite and ammonium sulfate, uniformly scratching, peeling, scratching for 120min, peeling, controlling water, and draining water and liquor by scratching;
3) washing to remove aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 34 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.3 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate, uniformly scratching, peeling, scratching for 40min, and scratching for draining;
4) dyeing and fixing color
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 65 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 0.6g/L of leveling agent, 5g/L of anhydrous sodium sulphate, 0.7g/L of dye and 1.5g/L of formic acid;
the operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate, uniformly scratching, throwing the skin, scratching for 15min, adding a dye, scratching for 40min, adding half formic acid, scratching for 30min, adding the remaining half formic acid, scratching for 30min, controlling water after the skin is taken out, draining and discharging the liquid;
5) aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: sodium bicarbonate 0.2g/L, sodium formate 0.4g/L, RESISTOL FST potent formaldehyde scavenger 2.0g/L
The operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, adding baking soda and sodium formate, uniformly scratching, throwing into skins, scratching for 10min, adding a formaldehyde scavenger, scratching for 30min, controlling water, throwing water, drying and finishing according to a conventional process, wherein the pH value is 4.0-4.5, and removing the skins.
The quality of the dyed raccoon fur is detected by the national quality supervision and inspection center of leather products.
The inspection basis is as follows: QB/T1284 & 2005 & lt & ltdetermination of azo dyes forbidden in leather and fur chemistry test & gt, GB/T19941-2005 & lt & gt determination of formaldehyde content in leather and fur chemistry test & lt & gt, QB/T1270 & lt 1991 & gt determination of elongation of finished fur & lt & gt, QB/T2711 & lt & gt 2005 & lt & gt determination of tearing force in leather physical and mechanical tests & lt: bilateral tear, QB/T2725-.
The judgment basis is as follows: reference to QB/T2923-
And (4) checking items: disablement of azo dyes, tear strength, elongation under load, odor, fastness of the skins to perspiration, free formaldehyde, shrinkage temperature, pH.
The results of the tests are shown in tables 3 and 4 below.
TABLE 3
TABLE 4
Note: the practical measurement data of 'not detected' in the forbidden azo dye project represents that the practical measurement value is less than or equal to 30 mg/kg; or when the content of the 4-aminobiphenyl and the 2-naphthylamine is more than 30mg/kg, the prior art can not determine, so the data is 'undetected'.
The detection results show that the quality of the raccoon fur products treated by the method meets the requirements, and particularly, the content of free formaldehyde is far better than the standard requirement, so the formaldehyde removing process is available.
Example 5 a method for removing free formaldehyde from fur by combined capturing, eluting and fixing, which is applied to the process of retanning and removing formaldehyde from natural-color raccoon fur
1) 50kg of raccoon fur, and 442.11mg/kg of free formaldehyde content measured by enterprises;
2) retanning and removing aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 40g/L, formic acid: 0.5g/L, 7g/L of ammonium alum, and powdery chrome tanning agent (HLS-C of Brother science and technology Co., Ltd., basicity 33%, chromic oxide content 25%): 13 g/L.
The operation is as follows: after the water temperature and water amount are adjusted, adding industrial salt and formic acid, uniformly scratching, peeling, scratching for 30min, adding ammonium alum and chrome tanning agent, and scratching for 60 min. After 5min of hourly stroke, 4 hours later, soda ash is added: 3g/L (dissolving soda with water 10 times of the amount of soda, adding the soda in three times, adding the soda once every 30 min), drawing for 30min, measuring the pH value to be 3.8-4.0 by using a pH meter, drawing for 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, drawing for 30min, standing overnight, drawing for 10min in the next morning, drawing the skin, and controlling the skin liquid to be in a drawing groove. Measuring the shrinkage temperature of the retanned leather board to 96 ℃, and grooving, draining water and draining liquid;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 4g/L, sodium hypochlorite: 0.2g/L, ammonium sulfate: 5 g/L.
The operation is as follows: after the water temperature and the water amount are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite, uniformly scratching, peeling, scratching for 120min, peeling, controlling water, and draining;
3) washing to remove aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 34 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.3 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate, uniformly scratching, peeling, scratching for 40min, and scratching for draining;
the content of free formaldehyde in the fur is 62.75mg/kg through enterprise detection.
4) Aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: RESISTOL FST potent formaldehyde scavenger 2g/L from Thompella Germany
The operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, adding a formaldehyde scavenger, uniformly scratching, throwing the skin, scratching for 30min, controlling the water, throwing the water, drying and finishing according to the conventional process, wherein the pH value is 5.0, and discharging the skin.
The free formaldehyde content of 62.75mg/kg is reduced to 13.28mg/kg again through enterprise detection.
Example 6A method for removing free formaldehyde from fur by combined use of trapping, elution and fixation is applied to the process of retanning and removing formaldehyde from natural-color raccoon fur
1) 50kg of raccoon fur, and 448.31mg/kg of free formaldehyde content measured by enterprises;
2) retanning and removing aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 34 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 38g/L, formic acid: 0.48g/L, 5g/L of ammonium alum and 15g/L of powdery chrome tanning agent.
The operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, adding ammonium alum and chrome tanning agent, and cutting for 60 min. After 5min of hourly stroke, 4 hours later, soda ash is added: 3g/L (dissolving soda by using water with 10 times of the amount of soda, adding the soda by three times, adding the soda once every 30 min), scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for 30min, standing overnight, scratching for 10min in the next morning, picking out the skin, controlling the skin upper liquid into a scratching groove, determining the shrinkage temperature of the retanning skin plate, reaching 97 ℃, and draining the liquid by scratching the groove;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 34 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 6g/L, sodium hypochlorite: 0.5g/L, ammonium sulfate: 5 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite on a cutting groove of equipment, uniformly cutting, peeling, cutting for 120min, discharging skin, controlling water, and draining the water;
3) washing to remove aldehyde
Equipment: cutting into 1000L slots, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 32 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.2 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 40min, draining and discharging water;
4) aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: RESISTOL FST potent formaldehyde scavenger from Germany Thompler corporation 1.5g/L
The operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, adding a formaldehyde scavenger, uniformly scratching, throwing the skin, scratching for 30min, adjusting the pH value to 4.8, peeling, controlling the water, throwing the water, drying and finishing according to the conventional process.
Through enterprise detection, the content of free formaldehyde is reduced from 448.31mg/kg to 11.80 mg/kg.
Example 7 method for removing free formaldehyde from fur by combination of capturing, eluting and fixing, which is applied to the process of retanning and removing formaldehyde from natural-color raccoon fur
1) 50kg of raccoon fur, and 441.21mg/kg of free formaldehyde content measured by enterprises;
2) retanning and removing aldehyde
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the temperature is 32 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: (main component sodium chloride) 30g/L, formic acid: 0.4g/L, 8g/L of ammonium alum and 10g/L of powdery chrome tanning agent.
The operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, adding ammonium alum and chrome tanning agent, and cutting for 60 min. After 5min every hour, 4 hours later, soda ash was added: 3g/L (dissolving soda by using water with 10 times of the amount of soda, adding the soda by three times, adding the soda once every 30 min), scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for 30min, standing overnight, scratching for 10min in the next morning, picking out the skin, controlling the skin upper liquid into a scratching groove, determining the shrinkage temperature of the retanning skin plate, reaching 100 ℃, and draining the liquid by scratching the groove;
2) capture removal of aldehydes
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 35 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 4g/L, sodium hypochlorite: 0.1g/L, ammonium sulfate: 3 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite on a cutting groove of equipment, uniformly cutting, peeling, cutting for 90min, discharging skin, controlling water, and draining the water;
3) washing to remove aldehyde
Equipment: cutting into 1000L slots, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 35 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.1 g/L.
The operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30min, draining and discharging water;
4) aldehyde fixation
Equipment: cutting a 1000L groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: RESISTOL FST potent formaldehyde scavenger of Germany Thompler company 1g/L
The operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, adding a formaldehyde scavenger, uniformly scratching, throwing the skin, scratching for 30min, adjusting the pH value to 4.5, peeling, controlling the water, throwing the water, drying and finishing according to the conventional process.
Through enterprise detection, the content of free formaldehyde is reduced from 441.21mg/kg to 10.50 mg/kg.
The quality of the dyed natural-color raccoon fur is detected by the national quality supervision and inspection center of leather products.
The inspection basis is as follows: QB/T1284 & 2005 & lt & ltdetermination of azo dyes forbidden in leather and fur chemistry test & gt, GB/T19941-2005 & lt & gt determination of formaldehyde content in leather and fur chemistry test & lt & gt, QB/T1270 & lt 1991 & gt determination of elongation of finished fur & lt & gt, QB/T2711 & lt & gt 2005 & lt & gt determination of tearing force in leather physical and mechanical tests & lt: bilateral tear, QB/T2725-.
The judgment basis is as follows: reference to QB/T2923-
And (4) checking items: disablement of azo dyes, tear strength, elongation under load, odor, fastness of the skins to perspiration, free formaldehyde, shrinkage temperature, pH.
The results of the tests are shown in tables 5 and 6 below.
TABLE 5
TABLE 6
Note: the practical measurement data of 'not detected' in the forbidden azo dye project represents that the practical measurement value is less than or equal to 30 mg/kg; or when the content of the 4-aminobiphenyl and the 2-naphthylamine is more than 30mg/kg, the prior art can not determine, so the data is 'undetected'.
The detection results show that the quality of the natural-color raccoon fur products treated by the method meets the requirements, and particularly, the free formaldehyde content is far superior to the standard requirement, so that the formaldehyde removing process is available.
TABLE 7 raw material information used in examples 1 to 7 of the present invention
According to QB/T1277-2012 determination of pH in the chemistry test of fur,
QB/T2925-2007 test method for color fastness to sunlight of fur,
QB/T2725-2005 leather odor determination,
GB/T19941.2-2019 determination of Formaldehyde content in leather and fur chemical test part 2: spectrophotometry (spectrophotometry),
GB/T19942.2-2019 determination of banned azo dyes in leather and fur chemical test,
GB/T1327-2019 leather surface color rubbing fastness test method,
QB/TI269-2012 determination of the tensile Strength and elongation of the physical and mechanical tests of the skins
QB/T1271-2012 determination of shrinkage temperature in physical and mechanical tests of skins
The successful research and development of the product not only further confirms the technical strength of enterprises, improves the technical research and development level of the enterprises, trains a batch of technical backbones of the enterprises, but also creates good economic benefits for the enterprises.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (10)
1. A method for removing free formaldehyde from fur through capture-elution-fixation combination is characterized by comprising the following steps:
1) weighing the fur containing free formaldehyde and needing to remove the aldehyde, and measuring the content of the free formaldehyde to be used as the basis of the water and chemical material usage amount in the following operation procedures;
2) retanning and removing aldehyde;
3) capturing and removing aldehyde;
4) washing and removing aldehyde;
5) dyeing and fixing;
6) and (4) aldehyde fixing operation.
2. The method for removing the free formaldehyde from the fur according to claim 1, wherein the specific steps of retanning and removing the formaldehyde are as follows:
preparing equipment: scratching a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 32-35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: 30-40g/L, formic acid: 0.4-0.5g/L, 5-8g/L of ammonium alum, powdery chrome tanning agent: 10-15 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and draining the liquid when the shrinkage temperature meets the requirement of more than 95 ℃.
3. The combined trapping-eluting-fixing process for removing free formaldehyde from skins as claimed in claim 1, wherein the trapping and removing process comprises the following steps:
preparing equipment: cutting a groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32-35 ℃, and the fur liquid B is prepared from the following raw materials in parts by weight: sodium metabisulfite: 4-6g/L, sodium hypochlorite: 0.1-0.5g/L, ammonium sulfate: 3-5 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, sodium pyrosulfite and ammonium sulfate are added into a groove of the equipment, the equipment is used for uniformly scratching, peeling is carried out, the equipment is used for scratching for 90-120min, the water is controlled after peeling, and the water is drained and drained.
4. The combined trapping-eluting-fixing method for removing free formaldehyde from fur according to claim 1, wherein the washing and formaldehyde removing steps are as follows:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 32-35 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.1-0.2 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate into a groove of the equipment, uniformly scratching, peeling, scratching for 30-60min, discharging the skin, controlling water, and draining the water.
5. The method for removing the free formaldehyde from the fur according to the claim 1, wherein the dyeing and fixing operation comprises the following steps:
preparing equipment: cutting a groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 60-65 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 0.5-1.0g/L of leveling agent, 5-10g/L of anhydrous sodium sulphate, 0.5-2 g/L of dye and 1.0-1.5g/L of formic acid; the operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 10-15min, adding a dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after skin emergence, and draining the water after cutting.
6. The method for removing free formaldehyde from fur according to claim 1, wherein the aldehyde fixing operation comprises the following steps:
preparing equipment: scratching a groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: 0.1-0.4g/L of baking soda, 0.1-0.4g/L of sodium formate and 1.5-3g/L of formaldehyde scavenger;
the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is scratched evenly, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 20-30min, the pH value is 3.6-5.0, the skin is taken out, the water is controlled, the water is thrown, and the drying and the finishing are carried out according to the conventional process.
7. The method for removing free formaldehyde from fur according to claim 1, wherein the steps of retanning and removing formaldehyde comprise:
preparing equipment: cutting a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: 40g/L, formic acid: 0.5g/L, 7g/L of ammonium alum, powdery chrome tanning agent: 13 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 h, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing out the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and requiring to reach more than 95 ℃.
8. A method for removing fur free formaldehyde by combination of capture, elution and fixation is characterized in that,
the method comprises the following steps:
1) weighing the fur containing free formaldehyde and needing to remove the aldehyde, and measuring the content of the free formaldehyde to be used as the basis of the water and chemical material usage amount in the following operation procedures;
2) retanning and removing aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: 40g/L, formic acid: 0.5g/L, 7g/L of ammonium alum, powdery chrome tanning agent: 13 g/L; the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing out the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and requiring to reach more than 95 ℃;
3) capturing and removing aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 4g/L, ammonium sulfate: 5 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium pyrosulfite and ammonium sulfate on a cutting groove of equipment, uniformly cutting, peeling, cutting for 90-120min, discharging the peel, controlling water, and draining the water;
4) washing to remove aldehyde:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 34 ℃, and the fur liquid C is prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.3 g/L;
the operation is as follows: after the water temperature and the water quantity are adjusted, adding sodium dodecyl sulfate on a cutting groove of the equipment, uniformly cutting, peeling, cutting for 30-60min, discharging the peel, controlling water, and draining the liquid in the cutting groove;
5) dyeing and fixing color:
equipment: cutting a groove, wherein the mass ratio of water to the fur liquid D is 20: 1, the temperature is 65 ℃, and the fur liquid D is mainly prepared from the following raw materials in parts by weight: 0.6g/L of leveling agent, 5g/L of anhydrous sodium sulphate, 0.7g/L of dye and 1.5g/L of formic acid;
the operation is as follows: after the water temperature and the water amount are adjusted, adding a leveling agent and anhydrous sodium sulphate on a cutting groove of the equipment, uniformly cutting, throwing the skin, cutting for 10-15min, adding a dye, cutting for 40min, adding half formic acid, cutting for 30min, adding the rest half formic acid, cutting for 30min, controlling water after skin discharge, and draining the water after cutting;
6) aldehyde fixation
Equipment: scratching a groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: 0.2g/L of baking soda, 0.4g/L of sodium formate and 2g/L of formaldehyde scavenger;
the operation is as follows: after the water temperature and the water amount are adjusted, baking soda and sodium formate are added into a groove of equipment, the equipment is scratched evenly, the skin is thrown and scratched for 10min, a formaldehyde scavenger is added, the scratching is carried out for 30min, the pH value is 4.0-4.5, the skin is taken out, the water is controlled, the water is thrown, and the drying and the finishing are carried out according to the conventional process.
9. A method for removing free formaldehyde from fur through capture-elution-fixation combination is characterized by comprising the following steps:
1) weighing the fur containing free formaldehyde and needing to remove the aldehyde, and measuring the content of the free formaldehyde to be used as the basis of the water and chemical material usage amount in the following operation procedures;
2) retanning and removing aldehyde:
equipment: scratching a groove, wherein the mass ratio of water to the fur liquid A is 20: 1, the set temperature is 32-35 ℃, and the fur liquid A is mainly prepared from the following raw materials in parts by weight: industrial salt: 30-40g/L, formic acid: 0.4-0.5g/L, 5-8g/L of ammonium alum, powdery chrome tanning agent: 10-15 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding industrial salt and formic acid on a device groove, uniformly scratching, peeling, scratching for more than 30min, adding ammonium alum and chrome tanning agent, scratching for more than 60min, scratching for more than 5min per hour, and adding soda ash after 4 hours: 3g/L, scratching for 30min, measuring the pH value by using a pH meter to be 3.8-4.0, scratching for more than 30min after the pH value meets the requirement, standing for more than 3 hours, heating to 38 ℃, scratching for more than 30min, standing overnight, scratching for 10min in the next morning, fishing out the skin, controlling the liquid on the skin into a scratching groove, measuring the shrinkage temperature of the retanned skin plate, and requiring to reach more than 95 ℃;
3) capturing and removing aldehyde:
equipment: cutting the groove, wherein the mass ratio of water to the fur liquid B is 20: 1, the temperature is 32-35 ℃, and the fur liquid B is mainly prepared from the following raw materials in parts by weight: sodium metabisulfite: 4-6g/L, sodium hypochlorite: 0.1-0.5g/L, ammonium sulfate: 3-5 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding sodium metabisulfite, ammonium sulfate and sodium hypochlorite into a cutting groove of equipment, uniformly cutting, peeling, cutting for 90-120min, and discharging and controlling water;
4) washing to remove aldehyde:
equipment: scratching a groove, wherein the mass ratio of water to the fur liquid C is 20: 1, the temperature is 32-35 ℃, and the fur liquid C is mainly prepared from the following raw materials in parts by weight: sodium dodecyl sulfate 0.1-0.2 g/L;
the operation is as follows: after the water temperature and the water amount are adjusted, adding sodium dodecyl sulfate into a scratch groove of the equipment, scratching uniformly, peeling, and scratching for 30-60 min;
5) aldehyde fixation
Equipment: scratching a groove, wherein the mass ratio of water to the fur liquid E is 20: 1, and the fur liquid E is mainly prepared from the following raw materials in parts by weight: 2.0g/L of formaldehyde scavenger;
the operation is as follows: the operation is as follows: after the water temperature and the water amount are adjusted, adding a formaldehyde scavenger, uniformly scratching, throwing the skin, scratching for 30 minutes at the pH value of 4.5-5.0, peeling, controlling water, throwing water, drying and finishing according to a conventional process.
10. The method for removing free formaldehyde from fur according to claim 1, 8 or 9, wherein the volume of the groove is 500-1000L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4211529A (en) * | 1977-09-03 | 1980-07-08 | Bayer Aktiengesellschaft | Chrome-tanning |
| AR248051A1 (en) * | 1990-12-19 | 1995-05-31 | Gaches Chimie Sa | Method for processing hides or leather, tanning agents and method for manufacturing same |
| CN104726621A (en) * | 2013-12-19 | 2015-06-24 | 浙江中辉皮草有限公司 | Fur free formaldehyde content reducing method |
| US20160251802A1 (en) * | 2013-12-25 | 2016-09-01 | Ningxia Wuzhong Jingyi Fur-Products Co., Ltd. | Cutting and double-face leather integrated dyeing process for tan sheep skin |
-
2021
- 2021-12-14 CN CN202111537297.1A patent/CN114540558A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4211529A (en) * | 1977-09-03 | 1980-07-08 | Bayer Aktiengesellschaft | Chrome-tanning |
| AR248051A1 (en) * | 1990-12-19 | 1995-05-31 | Gaches Chimie Sa | Method for processing hides or leather, tanning agents and method for manufacturing same |
| CN104726621A (en) * | 2013-12-19 | 2015-06-24 | 浙江中辉皮草有限公司 | Fur free formaldehyde content reducing method |
| US20160251802A1 (en) * | 2013-12-25 | 2016-09-01 | Ningxia Wuzhong Jingyi Fur-Products Co., Ltd. | Cutting and double-face leather integrated dyeing process for tan sheep skin |
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