CN104694675A - Novel process for manufacturing leather with simple procedures and equipment - Google Patents

Novel process for manufacturing leather with simple procedures and equipment Download PDF

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Publication number
CN104694675A
CN104694675A CN201310689868.2A CN201310689868A CN104694675A CN 104694675 A CN104694675 A CN 104694675A CN 201310689868 A CN201310689868 A CN 201310689868A CN 104694675 A CN104694675 A CN 104694675A
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China
Prior art keywords
waste liquid
liquid
minute
turns
storage tank
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CN201310689868.2A
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Chinese (zh)
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张壮斗
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Individual
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Individual
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Priority to CN201310689868.2A priority Critical patent/CN104694675A/en
Priority to PCT/CN2014/070730 priority patent/WO2015081624A1/en
Priority to US14/220,871 priority patent/US9776887B2/en
Priority to AU2014202826A priority patent/AU2014202826B2/en
Priority to BR102014012781A priority patent/BR102014012781A2/en
Priority to EP14002106.4A priority patent/EP2881369A1/en
Priority to NZ626503A priority patent/NZ626503B/en
Publication of CN104694675A publication Critical patent/CN104694675A/en
Priority to US15/723,146 priority patent/US10501336B2/en
Priority to US16/708,002 priority patent/US11040890B2/en
Pending legal-status Critical Current

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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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/04—Soaking
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/06—Facilitating unhairing, e.g. by painting, by liming
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes
    • 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
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries

Abstract

The invention provides a novel process for manufacturing leather with simple procedures and equipment. The novel process is characterized in that waste liquids from the procedures of pre-soaking, soaking, liming, reliming, deliming, softening, pickling, chroming, retanning, neutralizing and dyeing are recycled by steps in a totally closed manner. The novel process is used for manufacturing leather with simple procedures and equipment and has been implemented in the leather manufacturing room of Shangqiu Biosk Chemical Co., Ltd. and verified in actual large-scale production. The wastewater from the procedure of pre-soaking to the procedure of dyeing is recycled, thus the discharge of wastewater can be reduced greatly, and the problem of pollution from leather manufacturing can be solved thoroughly. In addition, the quality of the finished leather can be guaranteed, the loose grain rate of the finished leather can be reduced effectively, the compactness and fullness of the finished leather can be improved, chemical materials can be saved by 15-55%, a part of chemical materials can be saved by more than 90%, some chemical materials such as edible salt can be saved by 100%, and chromium powder can be saved by 35-65%.

Description

The novel leather-making technology that a kind of Processes and apparatus simplifies more
Technical field
The present invention relates to leather industry waste water circulation recycling field.
Background technology
In leather making process, adopt a large amount of industrial chemicals, as acid, alkali, salt, sulfide, lime, chrome tanning agent, fatting agent, dyestuff etc., wherein have quite a few to enter among waste water.Leather-making waste water mainly comes from preparation, tanning and other wet processing workshop sections.Account for more than 90% of total blowdown flow rate whole leather making process from pre-immersion to the blowdown flow rate of the production process of dyeing, its water quality characteristics is containing a large amount of complicated component and poisonous and harmful substances.Wherein containing a large amount of lime, salt, grease, ammonia nitriding compound, protein, sulfide, chromic salts, dyestuff, hairs, skin slag, silt etc., and COD, BOD are very high.Its pollutant kind is various, complicated component, and the large and foul smelling phenomenon of water quality and quantity variation factor is the trade effluent compared with refractory reason.
Along with the development of green technology equipment, current leather-making waste water has formed the treatment process (seeing the following form) of comparative maturity.But its operational process often spend high, efficiency is low, weak effect cannot reach real pollution treatment object.
Also there is people to carry out cycling and reutilization to leather-making waste water in our prior, but just simply cycling and reutilization has been carried out to the waste water of a certain operation, all very limited to the minimizing, the saving of material, the reduction of production cost etc. of quantity of wastewater effluent like this.The disposable whole recycling of waste water from pre-immersion to dyeing all process steps is realized if want, but be an extremely complicated scabrous problem, and often with the appearance of following problem: graywall rate of body weight gain, blue skin yield of leather all decline 1.5%-3.5%, shrinkage temperature declines 1.5 DEG C-3.5 DEG C, blue skin grain also can be made impaired, and grain is thicker, darkens, even produce " hair side " phenomenon, cause some performance index of finished leather not reach requirement.
Summary of the invention
Object of the present invention: realize the waste water circulation recycling from pre-immersion to dyeing all process steps; particularly liming and chrome tanning workshop section; waste liquid can recycle by iterative cycles; normal volatilization under removing state of nature and outside inevitably spilling; the rate of recovery of waste water can reach 100%; thoroughly solve a difficult problem for tanning sewage discharge, and this technical matters and equipment simplify more, are applicable to the existing large technological process of production of tannery.The resultant Leather property indices produced thus all reaches requirement, and effectively reduce finished leather loose side rate, improve the degree of packing of finished leather, fullness ratio, and can realize saving material 15%-55%, as saved chromium powder 35%-65%, part material can realize saving more than 90%, and indivedual material such as salt can realize saving 100%.
Technical scheme of the present invention is as follows:
The novel leather-making technology that a kind of Processes and apparatus simplifies more, it is characterized in that pre-immersion, main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning, retanning, in and, proceed step by step waste liquid circulation recycles in dyeing process, the waste liquid that each operation produces can not add special preparation process, also certain special preparation can be added, add-on is 0%-0.3% (taking waste liquid amount as radix), above-mentioned operation all realizes closed circulating, comprises the steps:
(1) the waste liquid circulation recycling of pre-soaking process: preimpregnation aqueous waste solution liquid storage tank or container for storing liquid are set on pre-soaking drum side, preimpregnation aqueous waste solution liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of pre-soaking process, stir, to be ready for use on down the pre-immersion of batch skin; The technique utilizing preimpregnation aqueous waste solution to carry out pre-immersion is: with raw hide weighing scale, 5%-300% preimpregnation aqueous waste solution, 0%-0.3% special preparation, and 0.2%-0.4% sterilant, turns 5-20 minute; 0.1%-0.8% Soaking, 0.1%-1.0% grease-removing agent, 0.05%-0.5% soda ash, turns 10-60 minute/stops 20-60 minute, turns and stops combination and carry out 2-8 time; Pre-immersion terminates waste liquid and enters liquid storage tank or container for storing liquid, answers the microbe population in periodic detection waste liquid, generally often circulates and detects once for two to three times;
(2) the waste liquid circulation recycling of main soaking process: main immersion waste liquid liquid storage tank or container for storing liquid are set on main soaking drum side, come to enter main immersion waste liquid liquid storage tank or container for storing liquid after solid substance in the waste liquid elimination waste liquid of autonomous soaking process, stir, to be ready for use on down the main immersion of batch skin; The technique utilizing main immersion waste liquid to carry out main immersion is: with raw hide weighing scale, the main immersion waste liquid of 5%-300%, 0%-0.3% special preparation, 0.1%-1.0% Soaking, 0.1%-0.8% grease-removing agent, 0.1%-1.0% soda ash, 0.05%-0.3%Na 2s, turns 30-80 minute/stops 10-50 minute, turns and stops combination and carry out 1-4 time; 0.1%-0.4% sterilant, turns 5-20 minute, then often turns 3-10 minute/stops 40-70 minute, spend the night; Next day turns 10-50 minute continuously; Main immersion terminates waste liquid and enters liquid storage tank or container for storing liquid, answers the microbe population in periodic detection waste liquid, generally often circulates and detects once for two to three times;
(3) the waste liquid circulation recycling of liming operation: Lime Liquor liquid storage tank or container for storing liquid are set on liming rotary drum side, Lime Liquor liquid storage tank or container for storing liquid is entered after solid substance from the Lime Liquor elimination waste liquid of liming operation, stir, to be ready for use on down the liming of batch skin; The technique utilizing Lime Liquor to carry out liming is: with raw hide weighing scale, 3%-200% spent lime liquor, 0%-0.3% special preparation, 0.2%-2.0% auxiliary liming agent, and 0.05%-1.5%NaHS, turns 20-40 minute; 0.3%-2.5% lime, turns 20-40 minute/stops 20-40 minute; 0.05%-1.5%NaHS, turns 10-30 minute/stops 10-30 minute; Start to filter hair; 0.05%-1.5%Na 2s, 0.3%-2.0% lime, 0.05%-0.5% grease-removing agent, turns 10-20 minute/stops 20-30 minute, turns and stops in conjunction with 2-4 time; 3%-200% spent lime liquor, 0%-0.3% special preparation, 0.1%-1.5%Na 2s, 0.2%-2.0% auxiliary liming agent, 0.3%-2.0% lime, 0%-0.2% liming enzyme, turns 10-30 minute/stops 10-30 minute, turns and stops in conjunction with 1-3 time, then turn 10-20 minute/stop 10-30 minute, turn stops combination and carries out 5-7 time; 3%-200% spent lime liquor, 0%-0.3% special preparation, turns 10-30 minute, then often turns 5-10 minute/stops 40-60 minute, spend the night; Liming terminates waste liquid and enters liquid storage tank or container for storing liquid, all needs Sodium Sulphide, Ca in chemical examination spent lime liquor before each use 2+equal size, in liming process, utilizes filter hair machine filter hair in time depending on the hair root degree that comes off;
(4) the waste liquid circulation recycling of multiple ash process: multiple grey waste liquid liquid storage tank or container for storing liquid are set on multiple grey rotary drum side, come to enter multiple grey waste liquid liquid storage tank or container for storing liquid after solid substance in the waste liquid elimination waste liquid of runback ash process, stir, to be ready for use on down the multiple ash of batch skin; The technique utilizing multiple grey waste liquid to carry out multiple ash is: with raw hide weighing scale, the multiple grey waste liquid of 3%-220%, 0%-0.3% special preparation, 0.2%-1.5% lime, 0.05%-1.0%Na 2s or NaHS, 0.1%-0.7% auxiliary liming agent, 0.05%-0.3%NaOH, turns 20-40 minute/stops 30-60 minute, then turns 5-20 minute/stops 30-60 minute, turns and stops combination and carry out 3-8 time, spend the night or directly go out drum; Multiple ash terminates waste liquid and enters liquid storage tank or container for storing liquid;
(5) the waste liquid circulation recycling of deashing and softening operation: deashing and softening waste liquid liquid storage tank or container for storing liquid are set on deashing and softening rotary drum side, deashing and softening waste liquid liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of deashing and softening operation, stir, to be ready for use on down the deashing and softening of batch skin; The technique utilizing deashing and softening waste liquid to carry out deashing and softening is: with graywall weighing scale, 3%-220% deashing and softening waste liquid, 0%-0.3% special preparation, 0.05%-0.45% grease-removing agent, 0.2%-1.5% deliming agent, 0.2%-1.5% ammonium sulfate, 0.05%-0.5% hydrochloric acid, 0.1%-0.5% acetic acid, turns 15-60 minute; 0-0.3% macerating enzyme, turns 15-40 minute; Deashing and softening terminates waste water and enters liquid storage tank or container for storing liquid, every circulation primary all should detect proteolytic enzyme in waste liquid and microbe population, proteolytic enzyme detects and preferably uses LC-MS instrument, also can using photoelectric colorimetry, determining the macerating enzyme quantity that should add according to detected result and the need of adding sanitas;
(6) the waste liquid circulation recycling of pickling chrome tanning process: pickling chroming waste liquor liquid storage tank or container for storing liquid are set on pickling chrome tanning rotary drum side, liquid storage tank is preferably deep to underground 2-8 rice and is beneficial to temperature control, preferably there are standby pool or tank, waste liquid liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of pickling chrome tanning process, stir, to be ready for use on down the pickling chrome tanning of batch skin, in pickling process, the add-on of salt is zero, also a small amount of (0%-5%) salt can be added or other has the material suppressing the swollen effect of acid, the technique utilizing chroming waste liquor to carry out pickling is: with graywall weighing scale, 3%-100% chrome wastewater, regulate the pH value of waste liquid to 0.3-5.0 with acid, 0%-0.3% special preparation, 0%-5% salt, 0.05%-0.3% mould inhibitor, turn 5-30 minute, 0%-2.0% formic acid or acetic acid or other organic acid, turn 5-40 minute, 0%-3.5% sulfuric acid or hydrochloric acid or other mineral acid, divide two to ten times equally and add, every minor tick 5-15 minute, turns 40-120 minute, 0%-1.0% fatting agent, turns about 30 minutes, stops 0.5-2 hour, also adjustable technique is: 0%-5% salt, and 0.05%-0.3% mould inhibitor, turns 5-30 minute, 0%-2.0% formic acid or acetic acid or other organic acid, turn 5-20 minute, 0.5%-2.0% sulfuric acid or hydrochloric acid or other mineral acid, 3%-100% chrome wastewater, 0%-0.3% special preparation, turns 70-120 minute, then carry out chrome tanning, technique is: 0.5%-2% chromium powder, turns 10-40 minute, 0.5%-3.5% chromium powder, turns 30-90 minute, 0.2%-1.2% sodium formiate or other salt, turn about 30 minutes, 0.10%-0.55% carries alkaline agent, turns 2.0-4.5 hour, 20%-80% chrome wastewater, 0%-0.3% special preparation, is warming up to 28 DEG C-42 DEG C in drum, adds rotary drum again or first chrome wastewater is added overall again in rotary drum intensification, turn 2-4 hour after being heated by chrome wastewater, chrome tanning terminates waste liquid and enters liquid storage tank or container for storing liquid, chromium from waste chromium content and pH value should be chemically examined at every turn, according to add-on and acid adding amount during tune waste liquid pH value of result of laboratory test determination chromium powder, also answer the microbe population in periodic detection waste liquid, general circulation detects once for three to five times, main detection mould quantity, according to the consumption of detected result determination mould inhibitor,
(7) the waste liquid circulation recycling of retanning procedures: retanning waste liquid liquid storage tank or container for storing liquid are set on retanning rotary drum side, retanning waste liquid liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of retanning procedures, stir, to be ready for use on down batch retanning of shaving leather; The technique utilizing retanning waste liquid to carry out retanning is: with shaving leather weighing scale, with hydrochloric acid or sulfuric acid or other acid, the pH value of retanning waste liquid is adjusted to 0.7-3.5,3%-250% retanning waste liquid, 0%-0.3% special preparation, temperature is adjusted to 32 DEG C-42 DEG C, 0.1%-0.5% formic acid or acetic acid, turn 20-50 minute; 0.5%-2.5% acrylic acid double tanning agent or other retanning agent, turn 10-40 minute; 0.5%-2.0% chromium powder, 0.1%-0.6% fatting agent, turns 30-90 minute; 0.5%-1.5% alkanoic, turns 20-50 minute; 0.3%-1.0% sodium formiate or sodium-acetate, 0.1%-0.5% sodium bicarbonate, turns 30-90 minute, then turns 10 minutes/stops 50 minutes, turns and stops combination and carry out 3-8 time, or stops drum and spend the night, pH value requirement 2.8-4.8; Retanning terminates waste liquid and enters liquid storage tank or container for storing liquid, should regularly chemically examine chromium from waste chromium content and pH value, the microbe population in periodic detection waste liquid, and general circulation detects once for three to five times;
(8) recycle with the waste liquid circulation of operation in: in and rotary drum is other arrange in and waste liquid liquid storage tank or container for storing liquid, in coming to enter after solid substance in the waste liquid elimination waste liquid of self-neutralization operation and waste liquid liquid storage tank or container for storing liquid, stir, to be ready for use on down batch neutralization of shaving leather; In utilization and the waste liquid technique of carrying out neutralizing be: with shaving leather weighing scale, in 3%-250% and waste liquid, 0%-0.3% special preparation, temperature is adjusted to 32 DEG C-35 DEG C, and in 1.0%-4.0% and tannin, 0.5%-3.5% sodium formiate, turns 20-40 minute; 0.2%-2.0% sodium bicarbonate, 0.5%-5.0% fatting agent, turns 30-60 minute, requires: pH value 4.0-6.5, the saturating heart of otch; Neutralization terminates waste liquid and enters liquid storage tank or container for storing liquid;
(9) dyeing process waste liquid circulation recycling: multiple waste liquid liquid storage tank or container for storing liquid are set on dyeing drum side, different color and luster adopts different liquid storage tanks or container for storing liquid, corresponding color and luster liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of dyeing process, stir, to be ready for use on down batch dyeing of shaving leather; Utilize the dyeing waste liquid technique of carrying out dyeing to be: with shaving leather weighing scale, 3%-200% dyes waste liquid, 0%-0.3% special preparation, and temperature is adjusted to 30 DEG C, and 0.5%-5.0% acrylic acid double tanning agent, turns 15-40 minute; 0.5%-6.0% double focusing cyanamide retanning agent, 0.5%-5.0% wattle extract, 0.5%-4.0% sulphiting vegetables oil, turns 30-60 minute; 0.5%-4.0% dyestuff, the compound fatting agent of 0.5%-5.0%, turns 40-80 minute, requires: the saturating heart of otch; Dyeing terminates waste liquid and enters same color and luster liquid storage tank or container for storing liquid.
In above-mentioned technique, each liquid storage tank or container for storing liquid are equipped with whipping appts (indivedual pond or tank also can hand mixing); Skin after pre-immersion and liming carries out fleshing and split, and the waste liquid produced in fleshing and split process is collected into corresponding pre-immersion and Lime Liquor liquid storage tank or container for storing liquid respectively in order to cycling and reutilization.Skin after pre-immersion, main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning, retanning, neutralization and dyeing process process removes conventional water wash step from, also can wash, and washing waste liquid is carried out cycling and reutilization, acid should be added when the washing waste liquid of recycle graywall its pH value is adjusted between 5-11.5.
Initial waste liquid used in the present invention comes from traditional pre-immersion, main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning, retanning, neutralization and dyeing process respectively, and the formation situation of various waste liquid is well known by persons skilled in the art; In general, immersion agent, NaCl, Na is contained in pre-immersion, main immersion waste liquid 2cO 3, grease-removing agent, grease and degradation production, hair, keratin protein, Saliva Orthana, meat, blood etc., wherein, generally, grease-removing agent content residual in waste liquid is generally the 15%-30% of initial content, immersion agent content residual in waste liquid is generally the 15%-25% of initial content, Na residual in waste liquid 2cO 3content is generally the 30%-50% of initial content; Containing grease and degradation production thereof, salt, lime, liming agent, S in liming, multiple grey waste liquid 2-, OH -, Na +, Ca 2+, protein and degradation production, enzyme and amine substance etc., wherein, generally, lime residual in waste liquid is generally the 37%-55% of initial content, Na residual in Lime Liquor 2s content is generally 2.4g/l-3.2g/l; Containing protein and degradation production, deliming agent, grease-removing agent, grease and degradation production thereof, enzyme and ammonium salt, amine substance etc. in deashing and softening waste liquid, wherein residual in waste liquid enzyme content is generally the 30%-50% of initial content, and amounts of ammonium salt residual in waste liquid is generally the 30%-40% of initial content; Containing Cr in chroming waste liquor 3+, Cl -, SO 4 2-, protein and degradation production, grease and degradation production thereof etc., wherein residual in waste liquid Cr 3+be generally 2.8g/l-3.2g/l, Cl -be generally 7g/l-15g/l, acid group content residual in waste liquid is generally the 30%-45% of initial content; Containing Na in retanning waste liquid +, Cr 3+and organic tanning agent etc.; In and in waste liquid containing neutral salt etc.; In dyeing process, employ the chemical materials such as fatting agent, the organic dyeing auxiliaries of dye well, except a part is absorbed, the overwhelming majority enters in waste water, and these pollutents all belong to larger molecular organics, and concentration is high, but biodegradation rate is very slow.If various waste liquid discharges arbitrarily above, not only great pollution is caused to environment, and the great wasting of resources can be produced.
Preferably, pre-immersion, main immersion and liming operation can adopt same rotary drum, arrange pre-immersion, main immersion and Lime Liquor liquid storage tank or container for storing liquid respectively, control rotary drum carry out discharging of waste liquid to each liquid storage tank or container for storing liquid in the mode of valve on rotary drum side; Specifically, when pre-immersion, main immersion and liming are with during with a rotary drum, rotary drum arranges valve 1, for preimpregnation aqueous waste solution is discharged into preimpregnation aqueous waste solution liquid storage tank or container for storing liquid, meanwhile, rotary drum arranges valve 2, for by main immersion discharging of waste liquid to main immersion waste liquid liquid storage tank or container for storing liquid, meanwhile, rotary drum arranges valve 3, for Lime Liquor is discharged into Lime Liquor liquid storage tank or container for storing liquid; During discharge preimpregnation aqueous waste solution, valve 1 is opened, and valve 2,3 is closed, and waste liquid is discharged into preimpregnation aqueous waste solution liquid storage tank or container for storing liquid through shunt conduit; When discharging main immersion waste liquid, valve 2 is opened, and valve 1,3 is closed, and waste liquid is discharged into main immersion waste liquid liquid storage tank or container for storing liquid through shunt conduit; During discharge Lime Liquor, valve 1,2 is closed, and valve 3 is opened, and waste liquid is discharged into Lime Liquor liquid storage tank or container for storing liquid through shunt conduit.
Similarly, deashing and softening and pickling chrome tanning process also can adopt same rotary drum, arrange deashing and softening and pickling chroming waste liquor liquid storage tank or container for storing liquid respectively rotary drum is other, control rotary drum carry out discharging of waste liquid to each liquid storage tank or container for storing liquid in the mode of valve; Specifically, when deashing and softening and pickling chrome tanning are with during with a rotary drum, rotary drum arranges valve 4, for by deashing and softening discharging of waste liquid to deashing and softening waste liquid liquid storage tank or container for storing liquid, simultaneously, rotary drum arranges valve 5, for pickling chroming waste liquor is discharged into pickling chroming waste liquor liquid storage tank or container for storing liquid.During discharge deashing and softening waste liquid, valve 4 is opened, and valve 5 is closed, and waste liquid is discharged into deashing and softening waste liquid liquid storage tank or container for storing liquid through shunt conduit; During discharge pickling chroming waste liquor, valve 4 is closed, and valve 5 is opened, and waste liquid is discharged into pickling chroming waste liquor liquid storage tank or container for storing liquid through shunt conduit.
Similarly, retanning, neutralization and dyeing process can adopt same rotary drum, rotary drum other arrange respectively retanning, in and and dyeing waste liquid liquid storage tank or container for storing liquid, control rotary drum in the mode of valve and carry out discharging of waste liquid to each liquid storage tank or container for storing liquid.Specifically, when retanning, neutralization and dyeing are with during with a rotary drum, rotary drum arranges valve 6, for by retanning discharging of waste liquid to retanning waste liquid liquid storage tank or container for storing liquid, meanwhile, rotary drum arranges valve 7, for will in and discharging of waste liquid in and waste liquid liquid storage tank or container for storing liquid, meanwhile, rotary drum arranges valve 8, for the discharging of waste liquid that will dye to dyeing waste liquid liquid storage tank or container for storing liquid.During discharge retanning waste liquid, valve 6 is opened, and valve 7,8 is closed, and waste liquid is discharged into retanning waste liquid liquid storage tank or container for storing liquid through shunt conduit; In discharge and waste liquid time, valve 7 is opened, and valve 6,8 is closed, and waste liquid is in shunt conduit is discharged into and waste liquid liquid storage tank or container for storing liquid; During discharge dyeing waste liquid, valve 6,7 is closed, and valve 8 is opened, and waste liquid is discharged into dyeing waste liquid liquid storage tank or container for storing liquid through shunt conduit.
In waste liquid circulation recycling process of the present invention, for pre-immersion, main immersion, liming, answer ash, deashing and softening, pickling chrome tanning, retanning, neutralization and these totally-enclosed waste liquid circulation that dye operation for, regularly process can be cleaned to waste liquid according to the sliminess of waste liquid in each waste liquid liquid storage tank or container for storing liquid, removing solids wherein, and regularly sterilize, microorganism in periodic detection waste liquid, proteolytic enzyme, pH value, chromium ion, calcium ion, sulfide and other related compounds, waste liquid continues cycling and reutilization.Such as, clean process by the mode of press filtration to waste liquid, be used for filling out hole or brickmaking or other purposes through the isolated useless solid thing of press filtration, isolated waste collection enters each waste liquid liquid storage tank or container for storing liquid in order to cycling and reutilization.The cycle cleaning process to waste liquid, comparatively traditional treatment method was long, and process is simpler and easy.
The present invention has following beneficial effect:
Present invention achieves in process hides from pre-immersion to the waste liquid circulation recycling of each operation of dyeing, and can recycle by iterative cycles, sewage effluent hardly, thoroughly solve a pollution in leather industry difficult problem, particularly utilize chrome wastewater, the fluid infusion in later stage heats up fewer than common process 3 DEG C-15 DEG C, saves the energy.This waste water circulation technique changes a little afterwards or does not add variation and is all applicable to the existing large technological process of production of tannery, and the resultant Leather property indices produced thus all reaches requirement, and effectively reduces finished leather loose side rate, improves the degree of packing of finished leather, fullness ratio.For traditional technology, Processes and apparatus simplifies more, can realize saving material 15%-55%, and as saved chromium powder 35%-65%, part material can realize saving more than 90%, and indivedual material such as salt can realize saving 100%.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic flow sheet of the novel leather-making technology that a kind of Processes and apparatus according to the present invention simplifies more.Note: the process of waste liquid can be carried out also can carrying out in rotary drum in liquid storage tank or container for storing liquid.
Embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the present invention is further described:
Embodiment 1
As shown in Figure 1, in pre-soaking process, after raw hide soaks in advance, be discharged into preimpregnation aqueous waste solution liquid storage tank after waste liquid elimination solid substance, stir, then extracted out by lye pump and be drained into pre-soaking drum, the technique utilizing preimpregnation aqueous waste solution to carry out pre-immersion is: with raw hide weighing scale, 200% preimpregnation aqueous waste solution, 0.15% special preparation, 0.25% sterilant, turns 15 minutes; 0.35% Soaking, 0.2% grease-removing agent, 0.2% soda ash, turns 20 minutes/stops 40 minutes, turns and stops combination and carry out 4 times; Pre-immersion terminates waste water and enters liquid storage tank; By fur fleshing, then carry out main immersion;
In main soaking process, main immersion waste liquid liquid storage tank is entered after main immersion waste liquid elimination solid substance, stir, then extracted out by lye pump and be drained into main soaking drum, the technique utilizing main immersion waste liquid to carry out main immersion is: with raw hide weighing scale, 200% main immersion waste liquid, 0.15% special preparation, 0.7% Soaking, 0.3% grease-removing agent, 0.5% soda ash, 0.1%Na 2s, turns 40 minutes/stops 40 minutes, turns and stops combination and carry out 3 times; 0.3% sterilant, turns 20 minutes, then often turns 3 minutes/stop 57 minutes, spend the night; Next day turns 40 minutes continuously; Main immersion terminates waste water and enters liquid storage tank;
In liming operation, Lime Liquor liquid storage tank is entered after Lime Liquor elimination solid substance, stir, then extracted out by lye pump and be drained into liming rotary drum, utilize Lime Liquor to carry out liming technique to be: with raw hide weighing scale, 70% spent lime liquor, 0.15% special preparation, 1.0% auxiliary liming agent, 0.15%NaHS, turns 30 minutes; 1.2% lime, turns 30 minutes/stops 30 minutes; 0.5%NaHS, turns 20 minutes/stops 20 minutes; Start to filter hair; 0.5%Na 2s, 0.8% lime, 0.1% grease-removing agent, turns 20 minutes/stops 30 minutes, turns and stops in conjunction with 3 times; 20% spent lime liquor, 0.15% special preparation, 0.5%Na 2s, 0.5% auxiliary liming agent, 1.0% lime, turns 20 minutes/stops 20 minutes, turns and stops in conjunction with 2 times; Then turn 10 minutes/stop 20 minutes, turn and stop in conjunction with 6 times; 80% spent lime liquor, 0.15% special preparation, turns 10 minutes; Then often turn 5 minutes/stop 55 minutes, spend the night; Liming terminates waste water and enters liquid storage tank; Graywall is carried out fleshing split, then carries out multiple ash;
In multiple ash process, enter multiple grey waste liquid liquid storage tank after multiple grey waste liquid elimination solid substance, stir, then extracted out by lye pump and be drained into liming rotary drum, the technique utilizing multiple grey waste liquid to carry out multiple ash is: with raw hide weighing scale, 100% multiple grey waste liquid, 0.15% special preparation, 0.8% lime, 0.2% sodium sulphite, 0.4% auxiliary liming agent, 0.10%NaOH, turns 30 minutes/stops 40 minutes, then often turn 5 minutes/stop 55 minutes, turn and stop combination and carry out 6 times, spend the night; Multiple ash terminates waste water and enters liquid storage tank;
In deashing and softening operation, deashing and softening waste liquid liquid storage tank is entered after deashing and softening waste liquid elimination solid substance, then extracted out by acid and alkali-proof pump and be drained into deashing and softening rotary drum, the technique utilizing waste liquid to carry out deashing and softening is: 100% deashing and softening waste liquid, 0.15% special preparation, 0.2% grease-removing agent, 0.6% deliming agent, 1.2% ammonium sulfate, 0.2% hydrochloric acid, 0.3% acetic acid, turns 40 minutes; 0.25% macerating enzyme, turns 30 minutes; Deashing and softening terminates waste water and enters liquid storage tank;
In pickling chrome tanning process, liquid storage tank is drained into after chrome wastewater elimination solid substance, its pH value is adjusted to be 0.7 with sulfuric acid, stir, then extracted out by acid proof pump and be drained into chrome tanning rotary drum, utilize chroming waste liquor to carry out pickling chrome tanning, in pickling process, the add-on of salt is zero, technique is: 90% chrome wastewater, 0.15% special preparation, 0.25% mould inhibitor, turns 10 minutes; 0.5% formic acid, turns 20 minutes; 0.3% sulfuric acid, divides three times equally and adds, and every minor tick 10 minutes, then turns 90 minutes; 0.2% fatting agent, turns 30 minutes, stops 1.5 hours; 1.8% chromium powder, turns 30 minutes; 2.2% chromium powder, turns 1 hour; 0.5% sodium formiate, turns 30 minutes; 0.25% carries alkaline agent, turns 4 hours; 80% chrome wastewater, 0.15% special preparation, is warming up to 35 DEG C, turns 3 hours; Chrome tanning terminates waste water and enters liquid storage tank;
In retanning procedures, retanning waste liquid liquid storage tank is entered after retanning waste liquid elimination solid substance, stir, then extracted out by acid proof pump and be drained into retanning rotary drum, utilize retanning waste liquid to carry out retanning process to be: with shaving leather weighing scale, with sulfuric acid, the pH value of retanning waste liquid is adjusted to 2.5,150% retanning waste liquid, 0.15% special preparation, temperature is adjusted to 36 DEG C, 0.3% formic acid, turns 30 minutes; 1.5% acrylic acid double tanning agent, turns 30 minutes; 1.0% chromium powder, 0.3% fatting agent, turns 60 minutes; 1.0% alkanoic, turns 30 minutes; 0.8% sodium formiate, 0.2% sodium bicarbonate, turns 60 minutes, then turns 10 minutes/stop 50 minutes, turns and stops combination and carry out 5 times, and pH value requires 2.8-4.8; Retanning terminates waste water and enters liquid storage tank;
In and operation in, in and waste liquid elimination solid substance after enter in and waste liquid liquid storage tank, stir, then by acid proof pump extract out be drained in and rotary drum, in utilization and waste liquid carry out in and technique be: in 200% and waste liquid, 0.15% special preparation, temperature is adjusted to 35 DEG C, in 2.0% and tannin, 1.5% sodium formiate, turns 20 minutes; 1.2% sodium bicarbonate, 3.0% fatting agent, turns 60 minutes, requires: pH value 4.0-6.5, the saturating heart of otch; Neutralization terminates waste water and enters liquid storage tank;
In dyeing process, same color and luster dyeing waste liquid liquid storage tank is entered after dyeing waste liquid elimination solid substance, stir, then extracted out by acid proof pump and be drained into dyeing drum, the technique utilizing dyeing waste liquid to carry out dyeing is: 80% dyeing waste liquid, 0.15% special preparation, and temperature is adjusted to 30 DEG C, 2.5% acrylic acid double tanning agent, turns 20 minutes; 4.0% double focusing cyanamide retanning agent, 1.5% wattle extract, 2.0% sulphiting vegetables oil, turns 40 minutes; 2.0% dyestuff, 1.5% compound fatting agent, turns 60 minutes, requires: the saturating heart of otch; Dyeing terminates waste water and enters same color and luster liquid storage tank;
The circulation waste liquid of above-mentioned pre-immersion, main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning, retanning, neutralization and dyeing process optionally regularly carries out press filtration process, the devil liquor recovery that press filtration obtains enters corresponding waste liquid pool and continues cycling and reutilization, and the useless solid thing that press filtration obtains is cheated or other for filling out.
When not departing from the present invention's spirit or substantive features, the present invention can be implemented in other forms, with reference to claim but not above-mentioned specification sheets, as instruction scope of the present invention.

Claims (17)

1. the novel leather-making technology that more simplifies of a Processes and apparatus, it is characterized in that pre-immersion, main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning, retanning, in and, proceed step by step waste liquid circulation recycles in dyeing process, the waste liquid that each operation produces can not add special preparation process, also certain special preparation can be added, add-on is 0%-0.3% (taking waste liquid amount as radix), above-mentioned operation all realizes closed circulating, comprises the steps:
(1) the waste liquid circulation recycling of pre-soaking process: preimpregnation aqueous waste solution liquid storage tank or container for storing liquid are set on pre-soaking drum side, preimpregnation aqueous waste solution liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of pre-soaking process, stir, to be ready for use on down the pre-immersion of batch skin; The technique utilizing preimpregnation aqueous waste solution to carry out pre-immersion is: with raw hide weighing scale, 5%-300% preimpregnation aqueous waste solution, 0%-0.3% special preparation, and 0.2%-0.4% sterilant, turns 5-20 minute; 0.1%-0.8% Soaking, 0.1%-1.0% grease-removing agent, 0.05%-0.5% soda ash, turns 10-60 minute/stops 20-60 minute, turns and stops combination and carry out 2-8 time; Pre-immersion terminates waste liquid and enters liquid storage tank or container for storing liquid, answers the microbe population in periodic detection waste liquid, generally often circulates and detects once for two to three times;
(2) the waste liquid circulation recycling of main soaking process: main immersion waste liquid liquid storage tank or container for storing liquid are set on main soaking drum side, come to enter main immersion waste liquid liquid storage tank or container for storing liquid after solid substance in the waste liquid elimination waste liquid of autonomous soaking process, stir, to be ready for use on down the main immersion of batch skin; The technique utilizing main immersion waste liquid to carry out main immersion is: with raw hide weighing scale, the main immersion waste liquid of 5%-300%, 0%-0.3% special preparation, 0.1%-1.0% Soaking, 0.1%-0.8% grease-removing agent, 0.1%-1.0% soda ash, 0.05%-0.3%Na 2s, turns 30-80 minute/stops 10-50 minute, turns and stops combination and carry out 1-4 time; 0.1%-0.4% sterilant, turns 5-20 minute, then often turns 3-10 minute/stops 40-70 minute, spend the night; Next day turns 10-50 minute continuously; Main immersion terminates waste liquid and enters liquid storage tank or container for storing liquid, answers the microbe population in periodic detection waste liquid, generally often circulates and detects once for two to three times;
(3) the waste liquid circulation recycling of liming operation: Lime Liquor liquid storage tank or container for storing liquid are set on liming rotary drum side, Lime Liquor liquid storage tank or container for storing liquid is entered after solid substance from the Lime Liquor elimination waste liquid of liming operation, stir, to be ready for use on down the liming of batch skin; The technique utilizing Lime Liquor to carry out liming is: with raw hide weighing scale, 3%-200% spent lime liquor, 0%-0.3% special preparation, 0.2%-2.0% auxiliary liming agent, and 0.05%-1.5%NaHS, turns 20-40 minute; 0.3%-2.5% lime, turns 20-40 minute/stops 20-40 minute; 0.05%-1.5%NaHS, turns 10-30 minute/stops 10-30 minute; Start to filter hair; 0.05%-1.5%Na 2s, 0.3%-2.0% lime, 0.05%-0.5% grease-removing agent, turns 10-20 minute/stops 20-30 minute, turns and stops in conjunction with 2-4 time; 3%-200% spent lime liquor, 0%-0.3% special preparation, 0.1%-1.5%Na 2s, 0.2%-2.0% auxiliary liming agent, 0.3%-2.0% lime, 0%-0.2% liming enzyme, turns 10-30 minute/stops 10-30 minute, turns and stops in conjunction with 1-3 time, then turn 10-20 minute/stop 10-30 minute, turn stops combination and carries out 5-7 time; 3%-200% spent lime liquor, 0%-0.3% special preparation, turns 10-30 minute, then often turns 5-10 minute/stops 40-60 minute, spend the night; Liming terminates waste liquid and enters liquid storage tank or container for storing liquid, all needs Sodium Sulphide, Ca in chemical examination spent lime liquor before each use 2+equal size, in liming process, utilizes filter hair machine filter hair in time depending on the hair root degree that comes off;
(4) the waste liquid circulation recycling of multiple ash process: multiple grey waste liquid liquid storage tank or container for storing liquid are set on multiple grey rotary drum side, come to enter multiple grey waste liquid liquid storage tank or container for storing liquid after solid substance in the waste liquid elimination waste liquid of runback ash process, stir, to be ready for use on down the multiple ash of batch skin; The technique utilizing multiple grey waste liquid to carry out multiple ash is: with raw hide weighing scale, the multiple grey waste liquid of 3%-220%, 0%-0.3% special preparation, 0.2%-1.5% lime, 0.05%-1.0%Na 2s or NaHS, 0.1%-0.7% auxiliary liming agent, 0.05%-0.3%NaOH, turns 20-40 minute/stops 30-60 minute, then turns 5-20 minute/stops 30-60 minute, turns and stops combination and carry out 3-8 time, spend the night or directly go out drum; Multiple ash terminates waste liquid and enters liquid storage tank or container for storing liquid;
(5) the waste liquid circulation recycling of deashing and softening operation: deashing and softening waste liquid liquid storage tank or container for storing liquid are set on deashing and softening rotary drum side, deashing and softening waste liquid liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of deashing and softening operation, stir, to be ready for use on down the deashing and softening of batch skin; The technique utilizing deashing and softening waste liquid to carry out deashing and softening is: with graywall weighing scale, 3%-220% deashing and softening waste liquid, 0%-0.3% special preparation, 0.05%-0.45% grease-removing agent, 0.2%-1.5% deliming agent, 0.2%-1.5% ammonium sulfate, 0.05%-0.5% hydrochloric acid, 0.1%-0.5% acetic acid, turns 15-60 minute; 0-0.3% macerating enzyme, turns 15-40 minute; Deashing and softening terminates waste water and enters liquid storage tank or container for storing liquid, every circulation primary all should detect proteolytic enzyme in waste liquid and microbe population, proteolytic enzyme detects and preferably uses LC-MS instrument, also can using photoelectric colorimetry, determining the macerating enzyme quantity that should add according to detected result and the need of adding sanitas;
(6) the waste liquid circulation recycling of pickling chrome tanning process: pickling chroming waste liquor liquid storage tank or container for storing liquid are set on pickling chrome tanning rotary drum side, liquid storage tank is preferably deep to underground 2-8 rice and is beneficial to temperature control, preferably there are standby pool or tank, waste liquid liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of pickling chrome tanning process, stir, to be ready for use on down the pickling chrome tanning of batch skin, in pickling process, the add-on of salt is zero, also a small amount of (0%-5%) salt can be added or other has the material suppressing the swollen effect of acid, the technique utilizing chroming waste liquor to carry out pickling is: with graywall weighing scale, 3%-100% chrome wastewater, regulate the pH value of waste liquid to 0.3-5.0 with acid, 0%-0.3% special preparation, 0%-5% salt, 0.05%-0.3% mould inhibitor, turn 5-30 minute, 0%-2.0% formic acid or acetic acid or other organic acid, turn 5-40 minute, 0%-3.5% sulfuric acid or hydrochloric acid or other mineral acid, divide two to ten times equally and add, every minor tick 5-15 minute, turns 40-120 minute, 0%-1.0% fatting agent, turns about 30 minutes, stops 0.5-2 hour, also adjustable technique is: 0%-5% salt, and 0.05%-0.3% mould inhibitor, turns 5-30 minute, 0%-2.0% formic acid or acetic acid or other organic acid, turn 5-20 minute, 0.5%-2.0% sulfuric acid or hydrochloric acid or other mineral acid, 3%-100% chrome wastewater, 0%-0.3% special preparation, turns 70-120 minute, then carry out chrome tanning, technique is: 0.5%-2% chromium powder, turns 10-40 minute, 0.5%-3.5% chromium powder, turns 30-90 minute, 0.2%-1.2% sodium formiate or other salt, turn about 30 minutes, 0.10%-0.55% carries alkaline agent, turns 2.0-4.5 hour, 20%-80% chrome wastewater, 0%-0.3% special preparation, is warming up in drum 28 DEG C-42 DEG C (add rotary drum after being heated by chrome wastewater again or first chrome wastewater is added overall again in rotary drum intensification), turns 2-4 hour, chrome tanning terminates waste liquid and enters liquid storage tank or container for storing liquid, chromium from waste chromium content and pH value should be chemically examined at every turn, according to add-on and acid adding amount during tune waste liquid pH value of result of laboratory test determination chromium powder, also answer the microbe population in periodic detection waste liquid, general circulation detects once for three to five times, main detection mould quantity, according to the consumption of detected result determination mould inhibitor,
(7) the waste liquid circulation recycling of retanning procedures: retanning waste liquid liquid storage tank or container for storing liquid are set on retanning rotary drum side, retanning waste liquid liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of retanning procedures, stir, to be ready for use on down batch retanning of shaving leather; The technique utilizing retanning waste liquid to carry out retanning is: with shaving leather weighing scale, with hydrochloric acid or sulfuric acid or other acid, the pH value of retanning waste liquid is adjusted to 0.7-3.5,3%-250% retanning waste liquid, 0%-0.3% special preparation, temperature is adjusted to 32 DEG C-42 DEG C, 0.1%-0.5% formic acid or acetic acid, turn 20-50 minute; 0.5%-2.5% acrylic acid double tanning agent or other retanning agent, turn 10-40 minute; 0.5%-2.0% chromium powder, 0.1%-0.6% fatting agent, turns 30-90 minute; 0.5%-1.5% alkanoic, turns 20-50 minute; 0.3%-1.0% sodium formiate or sodium-acetate, 0.1%-0.5% sodium bicarbonate, turns 30-90 minute, then turns 10 minutes/stops 50 minutes, turns and stops combination and carry out 3-8 time, or stops drum and spend the night, pH value requirement 2.8-4.8; Retanning terminates waste liquid and enters liquid storage tank or container for storing liquid, should regularly chemically examine chromium from waste chromium content and pH value, the microbe population in periodic detection waste liquid, and general circulation detects once for three to five times;
(8) recycle with the waste liquid circulation of operation in: in and rotary drum is other arrange in and waste liquid liquid storage tank or container for storing liquid, in coming to enter after solid substance in the waste liquid elimination waste liquid of self-neutralization operation and waste liquid liquid storage tank or container for storing liquid, stir, to be ready for use on down batch neutralization of shaving leather; In utilization and the waste liquid technique of carrying out neutralizing be: with shaving leather weighing scale, in 3%-250% and waste liquid, 0%-0.3% special preparation, temperature is adjusted to 32 DEG C-35 DEG C, and in 1.0%-4.0% and tannin, 0.5%-3.5% sodium formiate, turns 20-40 minute; 0.2%-2.0% sodium bicarbonate, 0.5%-5.0% fatting agent, turns 30-60 minute, requires: pH value 4.0-6.5, the saturating heart of otch; Neutralization terminates waste liquid and enters liquid storage tank or container for storing liquid;
(9) dyeing process waste liquid circulation recycling: multiple waste liquid liquid storage tank or container for storing liquid are set on dyeing drum side, different color and luster adopts different liquid storage tanks or container for storing liquid, corresponding color and luster liquid storage tank or container for storing liquid is entered after solid substance from the waste liquid elimination waste liquid of dyeing process, stir, to be ready for use on down batch dyeing of shaving leather; Utilize the dyeing waste liquid technique of carrying out dyeing to be: with shaving leather weighing scale, 3%-200% dyes waste liquid, 0%-0.3% special preparation, and temperature is adjusted to 30 DEG C, and 0.5%-5.0% acrylic acid double tanning agent, turns 15-40 minute; 0.5%-6.0% double focusing cyanamide retanning agent, 0.5%-5.0% wattle extract, 0.5%-4.0% sulphiting vegetables oil, turns 30-60 minute; 0.5%-4.0% dyestuff, the compound fatting agent of 0.5%-5.0%, turns 40-80 minute, requires: the saturating heart of otch; Dyeing terminates waste liquid and enters same color and luster liquid storage tank or container for storing liquid.
2. the large production and application of reality through Baosika's process hides workshop proves, this waste water circulation technique changes a little afterwards or do not add variation and is all applicable to the existing large technological process of production of tannery.
3. this waste water circulation technique resultant Leather loose side rate of producing is lower, fullness ratio is better, and can according to tannery's particular case Simplified flowsheet and equipment, if some factory is without place or appointed condition, liquid storage tank can not be dug, with container for storing liquid, also can process portion recycling waste water (only needing adjusting process parameter a little).
4. in actual production, according to field condition adopt drum outer pond in or in tank heating and cooling also can realize heating and cooling process in drum, used vapour is heated also can use electrically heated, and available overloading drum also can use conventional drum.
5. when this waste water circulation technique stainless steel rotary drum carries out pickling chrome tanning or stores waste liquid, do not increase metal (nickel, the chromium) content in waste liquid, if with new water, obviously increase the metal content in waste liquid and in leather, thus greatly shorten the life-span of stainless steel rotary drum, when cycle index increases, the consumption of zymin or other material suitably can be increased and decreased when main immersion or liming to obtain better effect.
6. the novel leather-making technology that more simplifies of a kind of Processes and apparatus as claimed in claim 1, it is characterized in that arranging multiple waste liquid liquid storage tank or container for storing liquid dyeing drum is other, different color and luster adopts different liquid storage tanks or container for storing liquid.
7. the novel leather-making technology that more simplifies of a kind of Processes and apparatus as claimed in claim 1, is characterized in that each liquid storage tank or container for storing liquid are provided with whipping appts, also can carry out hand mixing.
8. the novel leather-making technology that more simplifies of a kind of Processes and apparatus as claimed in claim 1, it is characterized in that the skin after immersion in advance and liming carries out fleshing and split, the waste liquid produced in fleshing and split process is collected into corresponding pre-immersion and Lime Liquor liquid storage tank or container for storing liquid respectively in order to cycling and reutilization.
9. the novel leather-making technology that more simplifies of a kind of Processes and apparatus as claimed in claim 1, it is characterized in that pre-immersion, main immersion and liming operation can adopt same rotary drum, on rotary drum side, pre-immersion, main immersion and Lime Liquor liquid storage tank or container for storing liquid are set respectively, control rotary drum with the mode of valve or other shunting mode and carry out discharging of waste liquid to each liquid storage tank or container for storing liquid, similar, deashing and softening and pickling chrome tanning process can adopt same rotary drum, and retanning, neutralization and dyeing process can adopt same rotary drum.
10. the novel leather-making technology that more simplifies of a kind of Processes and apparatus as claimed in claim 1, it is characterized in that regularly cleaning process to waste liquid according to the sliminess of waste liquid in each waste liquid liquid storage tank or container for storing liquid, by the mode of press filtration, process is cleaned to waste liquid, be used for filling out hole or brickmaking or other purposes through the isolated useless solid thing of press filtration, isolated waste collection enters each waste liquid liquid storage tank or container for storing liquid prepares against cycling and reutilization, the cycle cleaning process to waste liquid, comparatively traditional treatment method was long, and process is simpler and easy.
The novel leather-making technology that 11. a kind of Processes and apparatus as claimed in claim 1 simplify more, it is characterized in that the skin after immersion in advance, main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning, retanning, neutralization and dyeing process process removes conventional water wash step from, also can wash, and washing waste liquid is carried out cycling and reutilization, acid should be added when the washing waste liquid of recycle graywall its pH value is adjusted between 5-11.5.
The novel leather-making technology that 12. a kind of Processes and apparatus as claimed in claim 1 simplify more, it is characterized in that arranging standby pool or tank again at chroming waste liquor liquid storage tank or container for storing liquid side, other operation such as liming and deashing and softening operation etc. also can arrange standby pool or tank.
The novel leather-making technology that 13. a kind of Processes and apparatus as claimed in claim 1 simplify more, it is characterized in that the consumption of various chemical material and kind, waste liquid consumption, heating and cooling amplitude, operating time, working order, the adding indegree etc. and all can make according to user's particular case and significantly adjusting of waste liquid and chemical material, also other chemical material can be selected with alternative above-mentioned materials according to user's particular case.
The novel leather-making technology that 14. a kind of Processes and apparatus as claimed in claim 1 simplify more, it is characterized in that in liming process, filter hair machine filter hair is utilized in time depending on the hair root degree that comes off, as to do raw hide be goatskin, lamb skin and pigskin time, the removal of major part hair is carried out outside drum, and remaining part Mao Yike uses filter hair machine filter to go out in liming process.
The novel leather-making technology that 15. a kind of Processes and apparatus as claimed in claim 1 simplify more, it is characterized in that in pickling Chrome Tanning Process, the add-on of salt is 0, also can add the salt of a small amount of (0%-5%) or other has the material suppressing the swollen effect of acid.
The novel leather-making technology that 16. a kind of Processes and apparatus as claimed in claim 1 simplify more, is characterized in that total consumption of chromium powder is 2.0%-5.5%.
The novel leather-making technology that 17. a kind of Processes and apparatus as claimed in claim 1 simplify more, it is characterized in that the waste liquid that each operation produces can not add special preparation process, also can add certain special preparation, add-on is 0%-0.3% (taking waste liquid amount as radix).
CN201310689868.2A 2013-12-04 2013-12-04 Novel process for manufacturing leather with simple procedures and equipment Pending CN104694675A (en)

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CN201310689868.2A CN104694675A (en) 2013-12-04 2013-12-04 Novel process for manufacturing leather with simple procedures and equipment
PCT/CN2014/070730 WO2015081624A1 (en) 2013-12-04 2014-01-16 Tanning process
US14/220,871 US9776887B2 (en) 2013-12-04 2014-03-20 Tannery process with effluent recycling
AU2014202826A AU2014202826B2 (en) 2013-12-04 2014-05-22 Tannery process with effluent recycling
BR102014012781A BR102014012781A2 (en) 2013-12-04 2014-05-27 tanning process with wastewater recycling
EP14002106.4A EP2881369A1 (en) 2013-12-04 2014-06-18 Tannery process with effluent recycling
NZ626503A NZ626503B (en) 2013-12-04 2014-06-20 Tannery process with effluent recycling
US15/723,146 US10501336B2 (en) 2013-12-04 2017-10-02 Tannery process with effluent recycling
US16/708,002 US11040890B2 (en) 2013-12-04 2019-12-09 Tannery process with effluent recycling

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106839442A (en) * 2015-12-03 2017-06-13 孟州市东瑞机械设备有限公司 Two kinds of mode of heating constant temperature automatic circulation devices

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114231672A (en) * 2021-11-29 2022-03-25 无极县景森皮革制品有限公司 Leather pickling-free, salt-free and high-absorption chrome tanning process method
CN114214470B (en) * 2021-12-08 2023-10-27 兴业皮革科技股份有限公司 Pretreatment method of cattle vamp leather based on season transformation and application thereof
CN116516079A (en) * 2023-04-28 2023-08-01 中国水产科学研究院黄海水产研究所 Method for preparing blue wet leather by using puffer fish skin to preserve scales

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010100750A (en) * 2008-10-24 2010-05-06 Shoji Okuumi Pre-treatment method for tanning hide and method for tanning hide
CN102534056A (en) * 2010-12-14 2012-07-04 张壮斗 Tanning production process capable of recycling waste water repeatedly from soaking to dyeing

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100431986C (en) * 2004-12-31 2008-11-12 浙江卡森实业有限公司 Tanning technology for treatment and reuse of waste chrome liquor of bate without discharge and its treatment device
CN100360686C (en) * 2005-12-02 2008-01-09 四川大学 Clean production method of chromium-free automobile cushion leather
CN102120664B (en) * 2010-01-11 2014-04-09 张壮斗 Process for recycling tanning waste liquid by steps
CN101985668A (en) * 2010-05-04 2011-03-16 张壮斗 Leather making process for retanning by indefinitely recycling waste liquid
CN102559948B (en) * 2010-12-14 2015-05-20 张壮斗 Sheepskin leather making process with infinite cycling of waste liquid for liming (or restoring ash alkalinity)
CN102559950B (en) * 2010-12-14 2015-09-02 张壮斗 A kind of waste liquid that circulates carries out the leather-making technology of the large-scale production of pickling chrome tanning
CN102534055B (en) * 2010-12-14 2015-08-12 张壮斗 A kind of ashless or few grey liming dehairing process recycling spent lime liquor
CN102559949A (en) * 2010-12-14 2012-07-11 张壮斗 Novel leather producing process by pickling and chrome tanning by indefinitely circularly utilizing waste liquid without adding salt
CN102041321B (en) * 2010-12-24 2014-05-28 张壮斗 Leather manufacturing process by pickling and tanning salt-free and chrome-free recycled waste liquid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010100750A (en) * 2008-10-24 2010-05-06 Shoji Okuumi Pre-treatment method for tanning hide and method for tanning hide
CN102534056A (en) * 2010-12-14 2012-07-04 张壮斗 Tanning production process capable of recycling waste water repeatedly from soaking to dyeing

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106839442A (en) * 2015-12-03 2017-06-13 孟州市东瑞机械设备有限公司 Two kinds of mode of heating constant temperature automatic circulation devices

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