CN103320552B - Ultrasonic-assisted through-type four-bath chromium tanning method with separated penetration and fixation - Google Patents
Ultrasonic-assisted through-type four-bath chromium tanning method with separated penetration and fixation Download PDFInfo
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Abstract
The invention discloses an ultrasonic-assisted through-type four-bath chromium tanning method with separated penetration and fixation. The method completes chromium tanning through the following four steps: 1, mechanically extruding acidic leather until the acidic leather has certain moisture content and then allowing the acidic leather to enter into a penetrating fluid (a first bath) on which an ultrasonic wave field acts for penetration; 2, mechanically extruding a penetrated leather blank until the leather blank has certain moisture content and then allowing the leather blank to enter into a fixing fluid (a second bath) on which the ultrasonic wave field acts for fixation; 3, mechanically extruding the fixed leather blank until the leather blank has certain moisture content and then allowing the leather blank to enter into the penetrating fluid (a third bath) on which the ultrasonic wave field acts for penetration; and 4, mechanically extruding the penetrated leather blank until the leather blank has certain moisture content and then allowing the leather blank to enter into the fixing fluid (a fourth bath) on which the ultrasonic wave field acts for fixation; wherein the extruded penetrating fluid and the extruded fixing fluid are returned to a system for cycle use. According to the invention, continuous chromium tanning operation can be realized, and a blue wet leather blank meeting requirements can be obtained; the total time for tanning is only 4 to 20 min; the penetrating fluid and the fixing fluid can be easily recycled, so zero discharge of chromium tanning waste liquid is realized.
Description
Technical field
The invention belongs to leather tanning technical field, be specifically related to a kind of chromium and neutral salt zero release, infiltration, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method.
Background technology
Tanning is rawhide to be changed into the important procedure of leather, since Knapp invention chromic tanning in 1858, chrome tanned leather is owing to having the advantages such as higher hydrothermal stability, water-wash resistance and soft, leather body is plentiful, resistance to storage, always in tanning industry, especially light leather produce in dominate.By chrome tanning, can improve the performance of the shrinkage temperature of leather, resistance to enzymolysis, resistance to microbial process, be the basis that leather can carry out follow-up retanning, dyeing, stuffing and covering with paint.
Producing chrome-tanned main method is at present drum tanning method.This chrome tanning method because of every drum head operation amount large, chrome tanning process is relatively fixing, wet blue leather steady quality is the main chrome tanning method in present industrial production.But rotary drum chrome tanning can produce the leather-making waste water of a large amount of high-chromium amounts, high neutral salts contg, causes serious pollution and the wasting of resources.Continuous reinforcement along with people's environmental consciousness, much for reducing the method for chromium and neutral salt pollution, be developed, specifically have: 1. chroming waste liquor circulation utilization method (Wang Jun, Zhong Chonglin, Wang Qinghai etc. tannery's chroming waste liquor direct circulation utilizes and production practical technique research [J]. Chinese leather, 1997,26(4): 20-21; ), although the method is easy and simple to handle, practical, can reduce chromate waste water and neutral salt and pollute, chroming waste liquor recycle meeting reduces the quality of wet blue leather for a long time, and finally affects the quality of finished product leather, has larger limitation in use.2. non-aqueous media leather tanning.As leather chrome tanning in supercritical CO 2 medium, (Liao Longli, waits .CO for Zhang Weijuan, Feng Yuchuan
2supercutical fluid replaces the research [J] of water as medium chrome tanning and mechanism thereof, leather science and engineering, and 2003,13(4): 8-11,13(5): 16-19.).Though this class chrome tanning method has high chrome tanning agent utilization ratio, and chrome tanning medium easily reclaims, and because cost is high, support equipment lacks, and this class chrome tanning method only stays in laboratory stage at present, is difficult to realize industrialization promotion.3. acid-free chromte tannage technology.(Chen Zhanguang, Chen Wuyong, Zhang Zhaosheng. the applied research [J] of acid-free chromte tannage agent in ox-hide technique, Chinese leather, 2001,30(5): 13-15).Although this class process for tanning can avoid most neutral salt to pollute, in chroming waste liquor, chromium content also reduces greatly, still exists the pollution problem of chromium.
The tradition rotary drum chrome tanning method time is longer, at least needs 8h, have even need 2d more than, in recent years, in order to accelerate leather tanning process, process hides worker starts to utilize ultrasonic wave to aid in leather tanning operation.Because ultrasonic wave has cavatition, can produce the microenvironment of moment high temperature, high pressure, high energy, thereby can promote tanning agent infiltration, accelerate tannery, and can not cause chrome tanning agent chemical property change (stone is green for Peng Biyu, Sun Danhong. ultrasonic wave is on the impact of chrome tanning [J]. leather science and engineering, 2004,14(4): 7-12.).These researchs are all that to take the sour skin that common process produces be raw material skin, have studied the certain law in the interior ultrasonic wave leather tanning of longer tanning time (240min) process.Although these researchs have utilized ultrasonic wave auxiliary, but adopt drum tanning method, tanning time is still longer.
Summary of the invention
The object of the invention is the problem existing for prior art, provide a kind of infiltration, the fixedly separated auxiliary through type four of ultrasonic wave to bathe chrome tanning method.
To achieve the object of the present invention, contriver, on the basis of existing leather chrome tanning and the auxiliary disclosed method of tanning of ultrasonic wave, has furtherd investigate the impact for leather chrome tanning of Chrome Tanning Process, chrome tanned mechanics and ultrasonic wave.In Chrome Tanning Process, chrome tanning agent diffuses and penetrate into the whole square section of skin, then after pH raises, by coordinate bond, combines with collagen.The abundance of chrome tanning agent in skin square section and degree of uniformity determine by the penetration stage of chrome tanning, and chrome-tanned main chemical property is to determine in fixedly stage by chrome tanning.Summary is got up, and we can be divided into two portions by Chrome Tanning Process, i.e. infiltration is with fixing.Ultrasonic wave has cavatition, can accelerate the speed of a lot of chemical reactions.Research shows that ultrasonic wave can promote the infiltration of chrome tanning agent, but adopts separately ultrasonic wave to be difficult to reach in the short period of time (< 5min) requirement that chrome tanning agent is uniformly distributed in square section, shrinkage temperature is greater than 95 ℃.In order to accelerate the seepage velocity of chrome tanning agent and to make that chrome tanning agent is uniformly distributed at otch, shrinkage temperature is greater than 95 ℃, the inventor has explored again by mechanical force and has pushed and make to remove from office base moisture content and reduce, to accelerate the method for Chrome Tanning Process.
Mechanical presses has been removed in leather collagen fiber interfascicular gap after part moisture, can make capillary pipeline between the leather collagen fiber bundle vacuum state in microenvironment, this is for having elastic leather, at it, in the process of state before the recovering state after pushing extremely pushes, the air of trace can enter into leather inside.In the time of in the body lotion of the leather through mechanical presses in having ultrasonic acoustic field action, the micro-vacuum environment of inside, collegen filament gap, will cause ultrasonic cavitation threshold value to decline, thereby promote the generation of cavitation phenomenon.Meanwhile, the inner micro-vacuum environment of leather forming in mechanical presses process, is also conducive to the generation of the diffusion based on concentration difference.Leather base is carried out to the synergistic effect of hyperacoustic cavatition in mechanical presses and infiltration, fixation procedure, can greatly accelerate to permeate and fixing speed in Chrome Tanning Process, realize quick chrome tanning.
The inventor finds, only by first bath, permeate and second bathes fixing two and bathe and operate, and the shrinkage temperature of gained wet blue leather is lower than 90 ℃, Cr
2o
3content is less than 2 mg/g, and the thicker leather base of part is even difficult to tan, and chrome tanning effect can not meet leather and produce the requirement to wet blue leather.Therefore first bath infiltration and second bathe fixing after, the inventor has explored again by the 3rd and has bathed the methods that four fixing baths are bathed in infiltration and the 4th, Cr in discovery leather
2o
3content and shrinkage temperature can meet leather and produce the requirement to wet blue leather.By infiltration in Chrome Tanning Process, fixation procedure are separated, before permeating at every turn, fixing, adopt mechanical presses to reduce leather base moisture content, and in four bath processes of infiltration, fixing operation, use ultrasonic wave auxiliary, can realize in the short period of time (4-20min) and make that chrome tanning agent is uniformly distributed at the otch of leather, shrinkage temperature is greater than 95 ℃, Cr
2o
3the requirement of content>=3 mg/g.
The inventor has also explored in the infiltration and fixing basis that do not affect chrome tanning, adjusts the mechanical force extruding degree to leather base, and makes the penetrating fluid, the stationary liquid retrieval system recycle again that squeeze out, realizes the zero release of chromium and neutral salt in chrome tanning operating process.Infiltration in Chrome Tanning Process, fixedly stage separation, can make the recycle of chrome tanning agent, neutral salt and alkaline matter greatly simplify, to reducing chrome waste liquid and neutral salt discharge pollution on the environment has positive effect, also can reduce production costs, energy consumption simultaneously, economize on resources.
In order further to explore feasible processing condition and the inherent mechanism of action, the inventor also utilizes scanning electron microscope (SEM) to being squeezed to the leather base of different states and the histology of the wet blue leather that the inventive method is produced is studied, although find that leather is through mechanical presses and hyperacoustic effect, but grain pattern, square section and collegen filament braiding situation all with conventional wet blue leather no significant difference, illustrate that this novel method can not cause disadvantageous effect to the performance of leather, has higher feasibility.On the basis of above exploratory development, a kind ofly based on infiltration, the auxiliary through type four of fixedly separated ultrasonic wave, bathe chrome tanning methods and be developed.
Infiltration, the fixedly separated auxiliary through type four of ultrasonic wave are bathed a chrome tanning method, the method is characterized in that Chrome Tanning Process completes through following four steps:
(1), first bath operation: sour skin, enters in the penetrating fluid that contains neutral salt and chromium powder of ultrasonic wave field effect and permeates at least 1min to moisture content 40-60% through mechanical presses;
(2), second bathe operation: the leather base after infiltration to moisture content 40-60%, enters fixing at least 1min in the stationary liquid that contains basic material of ultrasonic wave field effect through mechanical presses;
(3), the 3rd bathe operation: the leather base after fixing again through mechanical presses to moisture content 40-60%, enter in the penetrating fluid that contains neutral salt and chromium powder of ultrasonic wave field effect and permeate at least 1min;
(4), the 4th bathe operation: the leather base after infiltration again through mechanical presses to moisture content 40-60%, enter ultrasonic wave field effect the stationary liquid that contains basic material in fixing at least 1min;
By four bath operations, can complete chrome tanning, after mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
In aforesaid method, the preferred version of each operation is: before first bath and the 3rd is bathed, to skin base mechanical presses to moisture content, be 40-60%, and more preferably 45-55%; The ultrasonic frequency adopting when four baths of permeating and fix are operated is 28kHz; First bath and the 3rd bathe in the mass percent of chromium powder be 10-30%, more preferably 15-25%; The mass percent of neutral salt is 3-8%, more preferably 4-7%; Infiltration temperature is 20-45 ℃, more preferably 25-35 ℃; Penetration time is 1-5min, more preferably 2-4min; Before the second bath and the 4th is bathed, to removing from office, to remove from office base moisture content after base mechanical presses be 40-60%, more preferably 45-55%; Second bathes and the mass concentration of the 4th bath neutral and alkali material is 0.5-2.5%, and more preferably 1-2%; Fixed temperature is 20-45 ℃, more preferably 25-35 ℃; Set time is 1-5min, more preferably 2-4min.
While permeating in above method, chromium powder used is chromium powder used in conventional tanning industry, is specifically as follows sugar reduction class chromium powder, sulphur dioxide reduction class chromium powder and Reduction by Thiosulfate class chromium powder.The neutral salt adding in penetrating fluid during infiltration is to rawhide collegen filament, to have the neutral salt of repression of swelling effect, and neutral salt comprises muriate, vitriol etc., and preferably neutral salt is at least one in sodium-chlor, Repone K, sodium sulfate, potassium sulfate.Basic material used in the time of fixedly can be for having alkaline salt or at least one in alkaloid compound, at least one in preferred ammoniacal liquor, sodium formiate, sodium-acetate, sodium bicarbonate, bicarbonate of ammonia, sodium carbonate, sodium hydroxide, potassium hydroxide.
Above-mentioned a kind of infiltration provided by the invention, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, utilize the ultimate principle of chrome tanning, at chrome tanning in earlier stage, cloudy, the neutral chromic compound of take permeates uniformly and is distributed between collegen filament as main chrome tanning agent, in the chrome tanning later stage, by putting forward alkali rising system pH, chromic compound coordination is also combined with collagen, completes tanning.By infiltration and fixation procedure are separated, utilize micro-vacuum environment in the leather base after mechanical presses and the synergistic effect of hyperacoustic cavatition, promoted the infiltration of chrome tanning agent to leather inside, subsequently the leather base after infiltration is being passed through to mechanical presses, utilize the synergistic effect of micro-vacuum environment and hyperacoustic cavatition in the leather base after mechanical presses, promote alkaline matter infiltration and with chromic compound coordination, be combined with collagen protein, complete the fixing of chrome tanning agent, permeate again subsequently, fixing operation once, adopt four baths to operate Chrome Tanning Process.Tanning sour skin used is pickling ox-hide, pickling goatskin, pickling lamb skin and pickling pigskin etc., the pH of acid skin is 2.0-3.0, acid skin thickness is 0.5-2mm, can meet conventional light leather in the market completely, as the needs of the light leather processing such as upper leather, shoe lining leather, sofa artificial leather, clothing leather to wet blue leather, and the square section chrome tanning agent of wet blue leather is evenly distributed, Cr
2o
3content>=3 mg/g, wet blue leather shrinkage temperature>=95 ℃.
The present invention has the following advantages:
1, method provided by the invention is skillfully constructed, technique and simple to operate, its major equipment used is mechanical presses device, with permeable tank and the pickup groove of ultrasonic generator, it is soluble that these are not only existing installation technology, and by lace curtaining travelling belt, these technique units are connected to (see photo), can realize the serialization of leather is permeated one by one, fixed to produce wet blue leather.
2, separated by by the infiltration in Chrome Tanning Process and fixing stage of method provided by the invention, can be by analyzing the chemical composition of penetrating fluid, stationary liquid and adding associated materials, realize simply the recycle of penetrating fluid, stationary liquid, realize the zero release of chromium and neutral salt, except reducing pollution, can also reduce production costs.
3, because the infiltration of method provided by the invention, fixed temperature are near room temperature, especially fixed temperature is put forward the temperature (40-45 ℃) of alkali well below routine, by hyperacoustic heat effect, can maintain the temperature of penetrating fluid, stationary liquid, do not need other energy to heat, therefore present method is not only energy-conservation, and can further reduce costs.
4, due to the infiltration of method provided by the invention with to fix for four required total times of bath be only 4-20min, compare with conventional Chrome Tanning Process is consuming time, tanning time shortens greatly, thereby tanning efficiency is high, and can also obtain the wet blue leather that various performances are different by the conversion of penetrating fluid and stationary liquid, to guarantee that chrome tanning operation can meet the requirement of market to different wet blue leather kinds.
5, because chromium powder that method provided by the invention is used, neutral salt and basic material etc. are conventional leather-making technology chemical materials used, wide material sources, workable.
6, by method provided by the invention, carry out chrome tanning, to the mechanical property of the operation of subsequent handling and finished leather and chemical property, all can not have a negative impact, by scanning electron microscopic observation, do not find that the method can cause disadvantageous effect to the fibrage of leather, grain pattern etc. yet, therefore, present method safety, reliable, practical.
Accompanying drawing explanation
Accompanying drawing is that the present invention was suitable for a kind ofly bathes the schematic diagram of chrome tanning square law devices based on infiltration, the fixedly separated auxiliary through type four of ultrasonic wave, a-extrusion roll wherein, b-transfer roller, c-permeable tank, d-ultrasonic generator, e-pickup groove.
Embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to the invention described above content and adjustment still belong to protection scope of the present invention.
Embodiment 1
To after pickling is processed, pH be 2.5 left and right, thickness is the sour skin for the production of Sheep Skin Upper Leather of 1.2mm, it is 40% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 5min in the penetrating fluid (first bath) that temperature is 20 ℃, contain 10% chromium powder and 4% sodium-chlor; By leather base mechanical presses to the moisture content after infiltration, being 40% left and right, is 28kHz in ultrasonic frequency, and temperature is (second bathes) fixing 1min in 20 ℃, the concentration sodium hydrogen carbonate solution that is 2%; Before infiltration, by leather base mechanical presses to the moisture content after fixing, be 40% left and right for the second time, then in ultrasonic frequency, be that 28kHz temperature is 20 ℃, permeate 5min in the penetrating fluid (the 3rd bathes) that contains 10% chromium powder and 8% sodium-chlor; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 45% left and right, is 28kHz in ultrasonic frequency, and temperature is fixing 1min in 20 ℃, the concentration sodium hydrogen carbonate solution (the 4th bathes) that is 2%; After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 2
To after pickling is processed, pH be 2.5 left and right, thickness is the sour skin for the production of goat upper leather for shoes of 1.2mm, it is 45% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 1min in the penetrating fluid (first bath) that temperature is 35 ℃, contain 30% chromium powder and 7% sodium sulfate; By leather base mechanical presses to the moisture content after infiltration, being 45% left and right, is 28kHz in ultrasonic frequency, and temperature is fixing 2min in 35 ℃, the concentration ammonia soln (second bathes) that is 1%; Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 55% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 2min in the penetrating fluid (the 3rd bathes) that temperature is 35 ℃, contain 20% chromium powder and 7% sodium sulfate; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 45% left and right, is 28kHz in ultrasonic frequency, and temperature is fixing 2min in 25 ℃, the concentration ammonium bicarbonate soln (the 4th bathes) that is 1%; After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 3
To after pickling is processed, pH be 3.0 left and right, thickness is the sour skin for the production of pig shoe lining leather of 0.5mm, it is 50% left and right that first machinery is squeezed to moisture content, in ultrasonic frequency, is then 28kHz, infiltration 1min in the penetrating fluid (first bath) that temperature is 45 ℃, contain 10% chromium powder and 3% Repone K; By leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, and temperature is fixing 1min in sodium carbonate solution 45 ℃, that concentration is 1.5% (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 50% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 1min in the penetrating fluid (the 3rd bathes) that temperature is 20 ℃, contain 20% chromium powder and 3% Repone K; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, and temperature is fixing 1min in 20 ℃, the concentration sodium carbonate solution (the 4th bathes) that is 1.5%; After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 4
To after pickling is processed, pH be 2.5 left and right, thickness is the sour skin for the production of cow leather upper leather of 2.0mm, it is 60% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 5min in the penetrating fluid (first bath) that temperature is 30 ℃, contain 20% chromium powder and 8% Repone K; By leather base mechanical presses to the moisture content after infiltration, being 60% left and right, is 28kHz in ultrasonic frequency, (second bathe) fixing 5min in the bicarbonate of ammonia that temperature is 30 ℃, concentration is 1% and 1.5% sodium formate solution; Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 60% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 3min in the penetrating fluid (the 3rd bathes) that temperature is 30 ℃, contain 25% chromium powder and 8% sodium-chlor; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, and fixing 5min in the bicarbonate of ammonia that temperature is 35 ℃, concentration is 1% and 0.5% sodium formate solution (the 4th bathes), bathes as the 4th; After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 5
To after pickling is processed, pH be 2.0 left and right, thickness is the sour skin for the production of sheep garment leather of 0.9mm, it is 45% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 4min in the penetrating fluid (first bath) that temperature is 25 ℃, contain 15% chromium powder and 5% potassium sulfate; By leather base mechanical presses to the moisture content after infiltration, being 55% left and right, is 28kHz in ultrasonic frequency, fixing 4min in the sodium-acetate that temperature is 25 ℃, concentration is 2.5% and 1.5% sodium formate solution (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 55% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 4min in the penetrating fluid (the 3rd bathes) that temperature is 25 ℃, contain 25% chromium powder and 5% potassium sulfate; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 45% left and right, is 28kHz in ultrasonic frequency, fixing 5min in the sodium-acetate that temperature is 45 ℃, concentration is 2% and 1.5% sodium formate solution (the 4th bathes); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 6
To after pickling is processed, pH be 2.0 left and right, thickness is the sour skin for the production of the positive suede clothing leather of pig of 1.1mm, it is 50% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 5min in the penetrating fluid (first bath) that temperature is 25 ℃, contain 15% chromium powder and 8% sodium sulfate; By leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, and temperature is fixing 1min in 25 ℃, the concentration sodium hydroxide solution (second bathes) that is 0.5%; Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 50% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 5min in the penetrating fluid (the 3rd bathes) that temperature is 20 ℃, contain 20% chromium powder and 4% sodium sulfate; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 2min in the sodium hydroxide solution that temperature is 25 ℃, concentration is 0.5% and 1% sodium acetate soln (the 4th bathes); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 7
To after pickling is processed, pH be 2.5 left and right, thickness is the sour skin for the production of goat upper leather for shoes of 1.2mm, it is 50% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 3min in the penetrating fluid (first bath) that temperature is 25 ℃, contain 25% chromium powder and 6% sodium-chlor; By leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the sodium bicarbonate that temperature is 25 ℃, concentration is 1.5% and 1% sodium formate solution (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 50% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 3min in the penetrating fluid (the 3rd bathes) that temperature is 25 ℃, contain 25% chromium powder and 6% sodium-chlor; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the sodium bicarbonate that temperature is 25 ℃, concentration is 1.5% and 1% sodium formate solution (the 4th bathes); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 8
To after pickling is processed, pH be 2.5 left and right, thickness is the sour skin for the production of yellow cow sofa leather of 1.8mm, it is 45% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 4min in the penetrating fluid (first bath) that temperature is 40 ℃, contain 30% chromium powder and 8% sodium-chlor; By leather base mechanical presses to the moisture content after infiltration, being 45% left and right, is 28kHz in ultrasonic frequency, fixing 4min in the bicarbonate of ammonia that temperature is 40 ℃, concentration is 1.5% and 2% sodium acetate soln (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 45% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 2min in the penetrating fluid (the 3rd bathes) that temperature is 30 ℃, contain 20% chromium powder and 8% sodium-chlor; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, be 45% left and right, in ultrasonic frequency, be 28kHz, fixing 4min in the bicarbonate of ammonia that temperature is 25 ℃, concentration is 1.5% and 2% sodium acetate soln (the 4th bathe), after mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 9
To after pickling is processed, pH be 2.0 left and right, thickness is the sour skin for the production of pig suede clothing leather of 1.2mm, it is 55% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 4min in the penetrating fluid (first bath) that temperature is 20 ℃, contain 15% chromium powder and 4% sodium sulfate; By leather base mechanical presses to the moisture content after infiltration, being 55% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the potassium hydroxide that temperature is 20 ℃, concentration is 0.5% and 2.5% sodium acetate soln (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 55% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 4min in the penetrating fluid (the 3rd bathes) that temperature is 30 ℃, contain 25% chromium powder and 6% sodium sulfate; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 45% left and right, is 28kHz in ultrasonic frequency, fixing 2min in the sodium hydroxide that temperature is 20 ℃, concentration is 0.5% and 1.5% sodium formate solution (the 4th bathes); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 10
To after pickling is processed, pH be 2.0 left and right, thickness is the sour skin for the production of goat leather for garment of 1.0mm, it is 50% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 4min in the penetrating fluid that temperature is 35 ℃, contain 10% chromium powder and 5% sodium-chlor (the 4th bathes); By leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the ammoniacal liquor that temperature is 35 ℃, concentration is 0.5% and 0.5% sodium carbonate solution (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 50% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 4min in the penetrating fluid (the 3rd bathes) that temperature is 30 ℃, contain 10% chromium powder and 5% sodium-chlor; By leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the ammoniacal liquor that temperature is 35 ℃, concentration is 1.5% and 1.5% sodium formate solution (the 4th bathe); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 11
To after pickling is processed, pH be 2.0 left and right, thickness is the sour skin for the production of ox clothing leather of 1.0mm, it is 50% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 3min in the penetrating fluid (first bath) that temperature is 20 ℃, contain 20% chromium powder and 7% sodium-chlor; By leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the sodium formiate that temperature is 20 ℃, concentration is 2.5% and 2.5% sodium acetate soln (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 50% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 3min in the penetrating fluid (the 3rd bathes) that temperature is 20 ℃, contain 20% chromium powder and 7% sodium-chlor; Before fixing for the second time, by leather base mechanical presses to the moisture content after infiltration, being 50% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the bicarbonate of ammonia that temperature is 35 ℃, concentration is 1.5% and 1.5% sodium acetate soln (the 4th bathes); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
Embodiment 12
To after pickling is processed, pH be 2.0 left and right, thickness is the sour skin for the production of ox upholstery leather of 2.0mm, it is 60% left and right that first machinery is squeezed to moisture content, then in ultrasonic frequency, be 28kHz, infiltration 3min in the penetrating fluid (first bath) that temperature is 35 ℃, contain 30% chromium powder and 5% sodium-chlor; By leather base mechanical presses to the moisture content after infiltration, being 60% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the sodium formiate that temperature is 35 ℃, concentration is 2% and 1% ammonium bicarbonate soln (second bathe); Before infiltration, by leather base mechanical presses to the moisture content after fixing, being 60% left and right for the second time, is then 28kHz in ultrasonic frequency, infiltration 3min in the penetrating fluid (the 3rd bathes) that temperature is 35 ℃, contain 20% chromium powder and 5% sodium-chlor; Before fixing for the second time, by leather mechanical presses to the moisture content after infiltration, being 60% left and right, is 28kHz in ultrasonic frequency, fixing 3min in the sodium formiate that temperature is 35 ℃, concentration is 2% and 1% ammonium bicarbonate soln (the 4th bathes); After mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
In above embodiment, the content of chromium powder, neutral salt and alkaline matter is mass percent.
In order to investigate the quality of wet blue leather that the present invention produces, contriver chooses the wet blue leather that above embodiment obtains at random, according to QB/T 2713-2005 standard test wet blue leather shrinkage temperatures, requires the shrinkage temperature of wet blue leather to be greater than 95 ℃; Adopt Potcrate method to measure the Cr in leather
2o
3content, requires the Cr of wet blue leather
2o
3content is greater than 3.00mg/g.The shrinkage temperature of gained wet blue leather and Cr
2o
3content sees the following form.
。
Claims (10)
1. infiltration, the fixedly separated auxiliary through type four of ultrasonic wave are bathed a chrome tanning method, the method is characterized in that Chrome Tanning Process completes through following four steps:
(1), first bath operation: sour skin, enters in the penetrating fluid that contains neutral salt and chromium powder of ultrasonic wave field effect and permeates at least 1min to moisture content 40-60% through mechanical presses;
(2), second bathe operation: the leather base after infiltration to moisture content 40-60%, enters fixing at least 1min in the stationary liquid that contains basic material of ultrasonic wave field effect through mechanical presses;
(3), the 3rd bathe operation: the leather base after fixing again through mechanical presses to moisture content 40-60%, enter in the penetrating fluid that contains neutral salt and chromium powder of ultrasonic wave field effect and permeate at least 1min;
(4), the 4th bathe operation: the leather base after infiltration again through mechanical presses to moisture content 40-60%, enter ultrasonic wave field effect the stationary liquid that contains basic material in fixing at least 1min;
By four bath operations, can complete chrome tanning, after mechanical presses recovery stationary liquid, operation is carried out retanning, dyeing, stuffing and covering with paint processing routinely, and the penetrating fluid wherein squeezing out, stationary liquid retrieval system recycle.
2. a kind of infiltration according to claim 1, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, in the method first bath and the 3rd bath, the mass percent of chromium powder is 10-30%, the mass percent of neutral salt is 3-8%, infiltration temperature is 20-45 ℃, and penetration time is 1-5min; The second bath and the 4th mass concentration of bathing neutral and alkali material are 0.5-2.5%, and fixed temperature is 20-45 ℃, and the set time is 1-5min.
3. a kind of infiltration according to claim 1 and 2, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, the method is 45-55% to leather base mechanical presses to moisture content before first bath and the 3rd is bathed infiltration, and in the second bath and the 4th, bathing before fixing is 45-55% to removing from office base mechanical presses to moisture content.
4. a kind of infiltration according to claim 1 and 2, the auxiliary through type four of fixedly separated ultrasonic wave are bathed chrome tanning methods, the method to the infiltration of leather base and fixedly time four ultrasonic frequencies of bathing the ultrasonic wave field adopting in operation be 28kHz.
5. a kind of infiltration according to claim 1 and 2, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, the method sour skin used is any one of pickling ox-hide, pickling goatskin, pickling lamb skin, pickling pigskin, the pH of acid skin is 2.0-3.0, and thickness is 0.5-2mm.
6. a kind of infiltration according to claim 1 and 2, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, in the method first bath and the 3rd bath, chromium powder is the conventional common chromium powder of tannery, mass percent is 15-25%, and the mass concentration of neutral salt is 4-7%; Infiltration temperature is 25-35 ℃, and penetration time is 2-4min.
7. a kind of infiltration according to claim 1 and 2, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, and the method second is bathed and the 4th mass concentration of bathing neutral and alkali material is 1-2%; Fixed temperature is 25-35 ℃, and the set time is 2-4min.
8. a kind of infiltration according to claim 1 and 2, the auxiliary through type four of fixedly separated ultrasonic wave are bathed chrome tanning methods, and the method neutral salt used is at least one in the neutral salt that can suppress rawhide collegen filament and expand; Basic material is to have alkaline salt or at least one in alkaloid compound.
9. a kind of infiltration according to claim 8, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, and the method neutral salt used is at least one in sodium-chlor, Repone K, sodium sulfate, potassium sulfate.
10. a kind of infiltration according to claim 8, the fixedly separated auxiliary through type four of ultrasonic wave are bathed chrome tanning method, and the method basic material used is at least one in ammoniacal liquor, sodium formiate, sodium-acetate, sodium bicarbonate, bicarbonate of ammonia, sodium carbonate, sodium hydroxide, potassium hydroxide.
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| CN107488760B (en) * | 2017-08-31 | 2020-02-28 | 四川大学 | Through type metal salt tanning method based on ultrasonic wave and microwave assistance |
| IT202200010121A1 (en) * | 2022-05-16 | 2023-11-16 | Remo Petroselli | MACHINERY FOR THE PROCESSING OF ANIMAL SKINS AND RELATED INDUSTRIAL PROCESS |
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