CN113278745A - Solid dispersion medium for anhydrous and low-water leather processing, preparation method and leather preparation process - Google Patents
Solid dispersion medium for anhydrous and low-water leather processing, preparation method and leather preparation process Download PDFInfo
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- CN113278745A CN113278745A CN202110553746.5A CN202110553746A CN113278745A CN 113278745 A CN113278745 A CN 113278745A CN 202110553746 A CN202110553746 A CN 202110553746A CN 113278745 A CN113278745 A CN 113278745A
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- dispersion medium
- solid dispersion
- leather
- plastic particles
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The application discloses a solid dispersion medium for anhydrous and little-water leather processing, a preparation method and a leather preparation process; the leather is characterized in that the solid dispersion medium is plastic particles and comprises the following components in parts by weight: 1-3 parts of EVA (ethylene vinyl acetate), 8-10 parts of POE (polyolefin elastomer), 0.1-0.3 part of color master batch, 0.3-1.0 part of stearic acid and 5-25% of 100-500-mesh ferromagnetic material. By adopting the solid dispersion medium, the preparation method and the leather preparation process, the problems that the mechanical action of the leather making is enhanced and the chemical materials are not uniformly dispersed in the rotary drum due to less bath and no bathe can be solved.
Description
Technical Field
The patent technology relates to a production and manufacturing process of leather, in particular to a solid dispersion medium for anhydrous and little-water leather processing, a preparation method and a leather preparation process.
Background
Most procedures of tanning processing are carried out under the condition of water, the water consumption is large, the water consumption can balance the advancement of the tanning process to a certain degree, the less the water consumption is, the tanning cost can be reduced to a certain extent, meanwhile, the discharge amount of sewage is reduced, and the environmental cost is also reduced. The water consumption of the tanning industry of developed countries is (30-60) m3The water consumption of the wet salted leather in the tanning industry of China is generally (60-80) m3One ton of salt wet leather, some tanneries can reach (40-50) m3T salt wet skin. The leather-making process is basically carried out in water, so that the water consumption is high. When chemical raw materials are added into bath liquid, the chemical raw materials cannot be completely absorbed by the raw material skin, and the absorption rate of some chemical raw materials is very low. In the traditional chrome tanning method, the absorption rate of leather to chrome tanning agent is generally 60-70%, and the concentration of trivalent chromium in chrome tanning waste liquid is higher, about 2000-3000 mg/L. In addition, synthetic organic matters such as fatting agents, retanning agents, auxiliaries and dyes are brought into wastewater in the processes of degreasing, softening, retanning, dyeing, fatliquoring and the like, and meanwhile, protein and grease in the raw hide also enter water as pollutants, and the organic matters which are difficult to biodegrade increase the difficulty of wastewater treatment.
For the problems, the flow washing is reduced or cancelled as much as possible in the production process, and the stuffy washing and flow washing method is adopted for the procedures requiring washing, so that the water can be saved, and the washing is clean. The turbid solution after the stuffy washing is directly discharged into a wastewater treatment tank; and discharging the clear liquid washed by running water into a recovery tank, storing, purifying and recycling. On the premise of meeting production requirements, the production water is reduced as much as possible, and the process operation is carried out in a way of 'less bath and no bath'. In the conventional process, after retanning, neutralization, dyeing and fatliquoring, filling and other treatments, washing and liquid changing are carried out, and the aim of the process is to overcome the negative influence caused by poor permeability and bonding performance of materials or poor compatibility. If the pre-tanning treatment is proper, the leather fibers are well dispersed, the probability that retanning agents, dyes, fatliquoring agents and the like penetrate into the leather and are combined with the leather fibers is increased, the absorption rate is increased, the neutralization retanning and dyeing fatliquoring can be carried out in one bath, materials with good permeation and absorption performance and good compatibility can be selected to be added in one bath or in sections, the working procedures are simplified, and materials and water are saved. The process route adopts 'deletion, subtraction and combination' and implements 'integrated process'. Such as: deashing and softening are integrated, retanning and neutralization are integrated, and the like.
The leather making process with less bath and no bath in the prior art is characterized in that: the liquor ratio refers to the weight of water used in a certain process and the weight ratio of the water to the leather in the wet processing of the leather. Obviously, the smaller the liquid ratio during processing, the more water is saved. Therefore, the small liquor ratio or even no bath is scientifically used in the tanning process, water can be saved, and the discharge amount of waste water can be reduced. In addition, the liquid ratio is reduced, so that the concentration of various chemical substances is increased, the absorption and utilization of chemical materials are facilitated, and the absorption rate is improved. But the liquid ratio is reduced, the mechanical action is enhanced, and the contact area and the contact opportunity of the leather and the drum body of the rotary drum are increased, so that the whole leather making process is improved, and the integral comprehensive balance is realized.
How to realize the minimum liquid ratio, namely, the water saving is always the key point of research and development in the leather manufacturing process.
Disclosure of Invention
The invention aims to provide a solid dispersion medium for anhydrous and low-water leather making in order to overcome the defects of the prior art.
Another object of the present invention is to provide a method for preparing a solid dispersion medium.
Still another object of the present invention is to provide a process for preparing leather.
The application develops a new generation of tanning auxiliary processing material on the basis of fully considering water conservation and reducing wastewater discharge. Most of water added in the conventional leather making process is only used as a medium and does not participate in the reaction, but a large amount of waste liquid is generated. The technology uses plastic particles to replace water, so that the mechanical action is moderate, part of the tanning processing workshop section can be completed under the action of a dispersion medium, and the production of the tanning processing waste liquid can be greatly avoided.
When the novel plastic granules developed by the application are used in a rotary drum as a solid dispersion medium, the extrusion effect of the leather can be increased, the dispersion and permeation of materials in the leather are promoted, and the uniformity of the concentration of the materials in the leather and between the leather can be ensured; meanwhile, the particles replace water to be used as a solid lubricant and are adsorbed on the surface of the leather, so that the friction force between the leather and the drum and the friction force between the leather and the drum are reduced, and the safety of leather making processing is ensured; in addition, the particles are insoluble in water, do not participate in reaction, can be repeatedly utilized, and are simple to put and collect. Solves the problems of strengthened mechanical action of the leather making machine of less bath and no bath and uneven dispersion of the chemical materials in the rotary drum.
A solid dispersion medium for use in waterless, low-water tanning processes, being plastic granules, comprising: 1-3 parts of ethylene-vinyl acetate copolymer Elastomer (EVA), 8-10 parts of polyolefin elastomer (POE), 5-25% of content of 100-500 mesh ferromagnetic material (Ferromagnetism (Ferromaganetestim) refers to the magnetic state of a material and has spontaneous magnetization phenomenon, the magnetism of transition group metal (such as iron) and alloy and compound thereof is called Ferromagnetism), 0.1-0.3 part of color master batch, 0.3-1.0 part of stearic acid, preferably 0.4-0.6 part of stearic acid.
Further, the ferromagnetic material may be any one or more of austenitic stainless steel (304), ferritic stainless steel (430, 446), martensitic stainless steel (410, 420, 430), and austenitic-ferritic (duplex) stainless steel (329).
A method for preparing a solid dispersion medium: 1-3 parts of EVA (ethylene vinyl acetate), 8-10 parts of POE (polyolefin elastomer), 0.1-0.3 part of color master batch, 5-25% of 100-500-mesh ferromagnetic material and 0.3-1.0 part of stearic acid; uniformly mixing the materials by using an internal mixer, then open-milling by using an open mill, and preparing plastic particles with the size of 2-5 mm by using a granulator; and (3) treating the plastic particles in a milling rotary drum for 2-5 h, removing ferromagnetic materials which are easy to fall off from the surfaces of the plastic particles, and then washing the plastic particles with water to obtain the solid dispersion medium.
A process for preparing leather, characterized in that it comprises, but is not limited to, the following steps: adding the evenly-shaved wet blue leather into a tanning rotary drum, adding a solid dispersion medium, a retanning agent, a fatting agent and a dye in several times, starting to rotate, then adding formic acid for fixation, continuing to rotate till the end, and drying to obtain crust leather. By weight of the shaved wet blue leather, 20-60% of plastic particles, 2-6% of retanning agent, 3-9% of fatting agent, 0.8-3.0% of dye and 2-3% of formic acid. The solid dispersion medium is recovered by magnetic force.
The beneficial effect of this application lies in:
(1) the first inventive concept of the present application is (basic concept) to propose a solid dispersion medium for waterless, low-water tanning process, which was developed according to the leather processing technology of the applicant, and specifically, a ferromagnetic material is added to plastic particles, and thus, can be recovered according to magnetic force.
(2) The second inventive concept of the present application is to provide a method for preparing the above-mentioned fixed dispersion medium, which has the technical difficulties that: in the preparation process of the plastic particles, the ferromagnetic material with the grain number of 100-500 is selected and evenly dispersed in the plastic particles.
The recyclable plastic particles suitable for different leather-making processing sections can be prepared by selecting ferromagnetic materials with different properties.
(3) The third inventive concept of the application is that when the leather is used in the rotary drum, the extrusion effect of the leather can be increased, the dispersion and permeation of the material in the leather are promoted, and the uniformity of the concentration of the material in the leather and between the leather and the leather can be ensured; meanwhile, the particles replace water to be used as a solid lubricant and are adsorbed on the surface of the leather, so that the friction force between the leather and the drum and the friction force between the leather and the drum are reduced, and the safety of leather making processing is ensured; in addition, the particles are insoluble in water, do not participate in reaction, can be repeatedly utilized, and are simple to put and collect.
Detailed Description
Preparation of plastic granules: 1-3 parts of EVA (ethylene vinyl acetate), 8-10 parts of POE (polyolefin elastomer), 0.1-0.3 part of color master batch, 5-25% of 100-500-mesh ferromagnetic material and 0.3-1.0 part of stearic acid; and (3) uniformly mixing the materials by using an internal mixer, then milling by using an open mill, and preparing plastic particles with the size of 2-5 mm by using a granulator. And (3) treating the plastic particles in a milling rotary drum for 2-5 h, removing ferromagnetic materials which are easy to fall off from the surfaces of the plastic particles, and then washing the plastic particles clean to obtain the solid dispersion medium for the anhydrous and low-water leather processing.
The parts are parts by weight.
Example 1: the preparation of ferromagnetic plastic particles selects one or more of ferrite stainless steel (430, 446), martensite stainless steel (410, 420, 430) and austenite-ferrite (biphase) stainless steel (329), can recover the plastic particles through magnetic force, and is mainly used for wet finishing sections such as retanning, neutralization, dyeing, greasing and the like in leather making.
Example 2: preparation of corrosion-resistant ferromagnetic particles, austenitic stainless steel (304) austenitic-ferritic (duplex) stainless steel (329), plastic particles can be recovered by magnetic force, and the method can be used for all leather-making sections.
Example 3:
the leather preparation process comprises the following steps: preparing sheepskin crust leather: using sheepskin blue wet leather, weighing 120% of the blue wet leather by weight, adding 200% of water, washing for 2 times, washing for 20 minutes each time, and discharging waste liquid; adding 30% of plastic particles (namely solid dispersion of the application), 2% of a neutralizing agent, 0.5h for conversion, 4% of a retanning agent, 0.5h for conversion, adding 4% of a fatliquoring agent (the fatliquoring agent is dissolved by using 20% of water at 35 ℃ and then added), heating the rotary drum to 50 ℃, and converting for 2.0 h; adding 1.5% dye (the dye is dissolved by 10% water and then added), and rotating for 2.0 h; adding 2% formic acid for fixation, and rotating for 30 min; washing with 200% water for 2 times, each for 20 min, and discharging waste liquid; and then drying to obtain crust leather.
The density of the plastic particles is 0.91g/cm3The size is 5.0mm, and the plastic particles can be directly used for next tanning after being recovered by magnetic force.
The invention is not limited to the examples, and any equivalent changes of the technical scheme of the invention by the persons skilled in the art after reading the description of the invention are covered by the claims of the invention. The above-mentioned embodiments are only for convenience of description, and are not intended to limit the present invention in any way, and those skilled in the art will understand that the technical features of the present invention can be modified or changed by other equivalent embodiments without departing from the scope of the present invention.
Claims (7)
1. A solid dispersion medium is characterized in that the solid dispersion medium is ferromagnetic plastic particles, the size of the plastic particles is 1-8 mm, the hardness of the plastic particles is 50-100A, and the content of a ferromagnetic material is 5-25%; the density of the solid dispersion medium is 0.80-1.1 g/cm3。
2. The solid dispersion medium of claim 1, wherein the solid dispersion medium comprises, by weight, 1 to 3 parts of EVA, 8 to 10 parts of POE, 100 to 500 mesh, 0.1 to 0.3 part of color masterbatch, 0.3 to 1.0 part of stearic acid, and the ferromagnetic material accounts for 5 to 25% of the system.
3. The solid dispersion medium according to claim 1 or 2, wherein the ferromagnetic material is any one or more of austenitic stainless steel, ferritic stainless steel, martensitic stainless steel, and austenitic-ferritic stainless steel.
4. The solid dispersion medium according to claim 1 or 2, wherein the size of the plastic particles is 2 to 5mm, the hardness of the plastic particles is 60 to 800A, and the mass of the ferromagnetic material is 10 to 15%.
5. The solid dispersion medium according to claim 1, wherein stearic acid is 0.4 to 0.6 part.
6. The method for preparing a solid dispersion medium according to claim 1, wherein the solid dispersion medium comprises, in parts by weight: 1-3 parts of EVA (ethylene vinyl acetate), 8-10 parts of POE (polyolefin elastomer), 0.1-0.3 part of color master batch, 0.3-1.0 part of stearic acid and 5-25% of a ferromagnetic material with 100-500 meshes by mass; uniformly mixing the materials by using an internal mixer, then open-milling by using an open mill, and preparing plastic particles with the size of 2-5 mm by using a granulator; and (3) treating the plastic particles in a milling rotary drum for 2-5 h, removing ferromagnetic materials which are easy to fall off from the surfaces of the plastic particles, and then washing the plastic particles with water to obtain the solid dispersion medium.
7. A process for preparing leather, comprising the steps of: adding pickled leather into a tanning rotary drum, adding a solid dispersion medium and a fatting agent in sequence, starting to rotate, then adding a chromium tanning agent, continuing to rotate, adding an alkali extracting agent, and continuing to rotate until tanning is finished to obtain chromium tanned leather; squeezing chrome tanned leather, shaving uniformly, putting into a rotary drum, adding a solid dispersion medium, starting to rotate, adding a retanning agent, a fatting agent and a dye in several times, finally adding formic acid for fixation, continuing to rotate till the end, and drying to obtain crust leather;
wherein the solid dispersion medium is the solid dispersion medium according to claim 1, 2, 3, 4 or 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110553746.5A CN113278745A (en) | 2021-05-20 | 2021-05-20 | Solid dispersion medium for anhydrous and low-water leather processing, preparation method and leather preparation process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110553746.5A CN113278745A (en) | 2021-05-20 | 2021-05-20 | Solid dispersion medium for anhydrous and low-water leather processing, preparation method and leather preparation process |
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| CN113278745A true CN113278745A (en) | 2021-08-20 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243182A (en) * | 2013-04-26 | 2013-08-14 | 四川大学 | Tanning method free of lime, sulfide, chloride ion and heavy metal chromium pollution |
| CN105671221A (en) * | 2015-07-08 | 2016-06-15 | 四川大学 | Cattle hide upper leather with double waterproof layers and preparation method thereof |
| CN110982958A (en) * | 2019-12-19 | 2020-04-10 | 中国皮革制鞋研究院有限公司 | Anhydrous chrome tanning process |
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- 2021-05-20 CN CN202110553746.5A patent/CN113278745A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243182A (en) * | 2013-04-26 | 2013-08-14 | 四川大学 | Tanning method free of lime, sulfide, chloride ion and heavy metal chromium pollution |
| CN105671221A (en) * | 2015-07-08 | 2016-06-15 | 四川大学 | Cattle hide upper leather with double waterproof layers and preparation method thereof |
| CN110982958A (en) * | 2019-12-19 | 2020-04-10 | 中国皮革制鞋研究院有限公司 | Anhydrous chrome tanning process |
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Application publication date: 20210820 |
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