CN103525955A - Tanning waste liquor stepwise recycling process with good effects - Google Patents
Tanning waste liquor stepwise recycling process with good effects Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
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- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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Abstract
The invention provides a tanning waste liquor stepwise recycling process with good effects. The process is characterized in that waste liquor is stepwise recycled in procedures of main soaking, liming, re-liming, de-liming softening and pickling for chrome tanning, wherein the waste liquor in all the procedures is recycled in a totally closed way; special preparations consisting of components such as sulfate, carbonate, silicate, acetate, protease and amino acid are added into the waste liquor in all the procedures, such as a series of products of Yishengbao ELIPO-S, ELIPO-L, ELIPO-D and Yishengbao 3 to facilitate the recycling of the waste liquor. According to the process, the waste liquor for the production from raw leather to wet blue leather is recycled, the quality of the wet blue leather can be ensured, the pollution control and chemical material cost are greatly reduced, and the discharge amount of sewage is greatly reduced.
Description
Technical field
The present invention relates to leather industry waste water circulation recycling field.
Background technology
Invention before us: a kind of Novel process for recycling waste leather-making liquid step by step does not carry out chemical treatment to waste liquid, the waste liquid producing for main immersion, liming, multiple ash, deashing and softening and pickling chrome tanning at present, after certain special preparation is processed, the protein etc. that can make to be unprofitable in waste liquid process hides is converted into useful composition or eliminates negative interaction.In addition, in liming process, the hair that filter hair machine filter goes out can produce economic benefit, such as processing grease-removing agent, fertilizer etc.
Production process from raw hide to blue skin is the heavily contaminated stage whole tanning production, and its blowdown flow rate accounts for total the more than 75% of blowdown flow rate in whole process hides process, and its water quality characteristics is to contain a large amount of complicated components and poisonous and harmful substances.Wherein contain a large amount of lime, protein, salt, grease, ammonia nitriding compound, sulfide, chromic salts, hairs, skin slag, silt etc., and COD, BOD are very high.Its pollutant kind is various, complicated, and the large and foul smelling phenomenon of water quality and quantity variation factor, is compared with the trade effluent of refractory reason.
Along with the development of green technology equipment, leather-making waste water has formed the treatment process (seeing the following form) of comparative maturity at present.But that its operational process often spends is high, efficiency is low, weak effect cannot reach real pollution treatment object.
Before us, also there is people to carry out cycling and reutilization to leather-making waste water, but just simply the waste water of a certain operation has been carried out to recycle, all very limited to reduction of the saving of the minimizing of quantity of wastewater effluent, material, production cost etc. like this.If want, realize the disposable whole recyclings of waste water from raw hide to all workshop sections of blue skin, but be an extremely complicated scabrous problem, and often follow the appearance of following problem: graywall rate of body weight gain, the blue skin yield of leather 1.5%-3.5% that all declines, shrinkage temperature declines 1.5 ℃-3.5 ℃, also can make blue skin grain impaired, grain chap, darkens, and even produces " hair side " phenomenon.
Summary of the invention
Object of the present invention: realize the cycling utilization of wastewater from raw hide to blue skin all process steps; particularly liming and chrome tanning workshop section; waste liquid can unlimitedly recycle; outside removing the normal volatilization under state of nature and inevitably spilling; the rate of recovery of waste liquid can reach 100%, and guarantees blue cortex amount, makes blue skin yield of leather increase 1%-3.5%; shrinkage temperature improves 3 ℃-12 ℃ (comparing with common process), has obtained the blue skin of high-quality.The finished product leather property indices of producing thus all reaches requirement, and effectively reduces finished leather loose side rate, has improved the degree of packing of finished leather.And can realize and save material 15%-55%, as saved chromium powder 40%-50%, part material can realize saves more than 90%, and indivedual materials can realize and save 100% as salt, reduce this stage sewage discharge 75%-90%.
Technical scheme of the present invention is as follows:
A kind of process for recycling waste leather-making liquid step by step of better effects if, it is characterized in that proceed step by step waste liquid cycling and reutilization in main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning process, the waste liquid that each operation produces adds certain special preparation, add-on is 0.05%-0.3% (take waste liquid amount as radix), and above-mentioned operation all realizes closed circulating.Comprise the steps:
(1) the waste liquid cycling and reutilization of main soaking process: main immersion waste liquid liquid storage tank is set on main soaking drum side, in the waste liquid elimination waste liquid of next autonomous soaking process, after solid substance, enter main immersion waste liquid liquid storage tank, stir, to be ready for use on down the main immersion of batch skin; The technique of utilizing main immersion waste liquid to carry out main immersion is: with raw hide weighing scale, add the main immersion waste liquid of 70%-250%, 0.05%-0.3% special preparation, turn 5-15 minute; 0.1%-1.0% Soaking, 0.1%-0.8% grease-removing agent, 0.1%-1.0% soda ash, 0.05%-0.3% Sodium Sulphide, turn 30-80 minute, stops 10-50 minute, turns and stop in conjunction with carrying out 1-4 time; 0.1%-0.4% sterilant, turns 5-20 minute, spends the night; Turn continuously 10-50 minute next day, main immersion finishes waste water and enters liquid storage tank.Should regularly detect the microbe population in waste liquid, general every circulation detects once for two to three times.
(2) the waste liquid cycling and reutilization of liming operation: on liming rotary drum side, Lime Liquor liquid storage tank is set, from entering Lime Liquor liquid storage tank after solid substance in the Lime Liquor elimination waste liquid of liming operation, stirs, to be ready for use on down the liming of batch skin; The technique of utilizing Lime Liquor to carry out liming is: with raw hide weighing scale, add 20%-90% Lime Liquor, 0.05%-0.3% special preparation, turn 5-15 minute; 0.15%-0.3% grease-removing agent, 0.1%-0.5% Sodium sulfhydrate, turn 10-40 minute, stops 5-15 minute, turns and stop in conjunction with carrying out 3-6 time; 30%-90% Lime Liquor, 0.05%-0.3% special preparation, 0.2%-1.0% lime, 0.2%-0.6% sodium sulphite, 0.2%-0.5% Sodium sulfhydrate, 0.3%-1.5% liming agent, turn 10-50 minute, stops 5-30 minute, turns and stop in conjunction with carrying out 1-3 time; Filter hair 1-3 hour; 20%-60% Lime Liquor, 0.05%-0.3% special preparation, 0.2%-1.0% sodium sulphite, 0.05%-0.4% sodium hydroxide, 0.1%-0.8% liming agent, turn 30-90 minute, stops 10-40 minute, turns and stop in conjunction with carrying out 2-4 time; Add 10%-20% clear water, 0.5%-2.0% lime, turn and stop each 10-40 minute, then often turn 5-10 minute and stop 20-40 minute, carry out 2-4 time, then often turn 5-10 minute and stop 30-120 minute, spend the night; Before each use, all need to chemically examine Sodium Sulphide in spent lime liquor, Ca
2+equal size.In liming process, depending on the hair root degree that comes off, utilize in time filter hair machine filter hair;
(3) the waste liquid cycling and reutilization of multiple ash process: multiple grey waste liquid liquid storage tank is set multiple grey rotary drum is other, comes to enter multiple grey waste liquid liquid storage tank 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 criticizing skin; The technique of utilizing multiple grey waste liquid to carry out multiple ash is: with raw hide weighing scale, add the multiple grey waste liquid of 70%-220%, 0.05%-0.3% special preparation, turn 5-15 minute; 0.2%-1.5% lime, 0.05%-1.0%Na
2s (or NaH S), 0.1%-0.7% liming agent, 0.05%-0.3% caustic soda, turned about 30 minutes, stops 30-60 minute, turns 5-20 minute and stop 30-60 minute (being total to 3-8 time repeatedly), spends the night or directly go out drum; Multiple ash finishes rear waste water and enters liquid storage tank, lime-fleshing, split;
(4) the waste liquid cycling and reutilization of deashing and softening operation: at the other deashing and softening waste liquid liquid storage tank that arranges of deashing and softening rotary drum, from entering deashing and softening waste liquid liquid storage tank after solid substance in 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 of utilizing deashing and softening waste liquid to carry out deashing and softening is: with graywall weighing scale, add 30%-220% deashing and softening waste liquid, 0.05%-0.3% special preparation, turn 5-15 minute; 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, turn 15-60 minute; 0%-0.3% macerating enzyme, turns 15-40 minute.Deashing and softening finishes rear waste water and enters liquid storage tank.Every circulation primary all should detect proteolytic enzyme and the microbe population in waste liquid, and proteolytic enzyme detects and preferably uses LC-MS instrument, also can use photoelectric colorimetry, according to detected result, determines the macerating enzyme quantity that should add and whether needs to add sanitas;
(5) the waste liquid cycling and reutilization of pickling chrome tanning process: on pickling chrome tanning rotary drum side, chroming waste liquor liquid storage tank is set, this pond is preferably deep to underground 2-8 rice in order to temperature control, and preferably has standby pool.From entering chroming waste liquor liquid storage tank after solid substance in the waste liquid elimination waste liquid of chrome tanning process, after cooling, with acid, regulate the pH value of chroming waste liquor to 0.2-1.2, stir, to be ready for use on down the pickling chrome tanning of batch skin.The technique of utilizing chroming waste liquor to carry out pickling chrome tanning is: with graywall weighing scale, add 20%-100% chroming waste liquor, 0.05%-0.3% special preparation, 0.1%-0.4% mould inhibitor, 0%-5% salt or other material that has inhibition acid to swell and act on, turn 5-30 minute; 0.3%-0.6% formic acid, turns 10-40 minute; 0.2%-0.7% sulfuric acid, divides two to four times equally and adds, and every minor tick 5-30 minute, turns 70-100 minute; 0%-0.5% fatting agent, turns 15-50 minute, stops 1-2 hour; 0.5%-3.0% chromium powder, turns 20-60 minute; 0.5%-3.0% chromium powder, turns 0.5-2.0 hour; 0.1%-0.7% sodium formiate, turns 15-55 minute; 0.15%-0.45% carries alkaline agent, turns 2.0-5.5 hour; Add 20%-80% chroming waste liquor, 0.05%-0.3% special preparation, turn 5-15 minute; After be warming up to 28 ℃-38 ℃, turn 2-5 hour.Should regularly chemically examine chromium content and pH value in useless chrome liquor.Should regularly detect the microbe population in waste liquid, generally circulate and detect once for three to five times, mainly detect mould quantity, according to detected result, determine the consumption of mould inhibitor.
In above-mentioned technique, certain special preparation is as prebiotic precious series product: ELIPO-S, ELIPO-L, ELIPO-D, prebiotic precious 3.These special preparations are grouped into by one-tenth such as vitriol, carbonate, silicate, acetate, proteolytic enzyme, amino acid.The protein etc. that can make to be unprofitable in waste liquid process hides after special preparation is processed is converted into beneficiating ingredient or eliminates negative interaction.
In above-mentioned technique, each liquid storage tank is equipped with whipping appts (indivedual ponds also can hand mixing).The waste collection producing in lime-fleshing and split process enters liming or multiple grey waste liquid liquid storage tank is prepared against cycling and reutilization.Micromicro after immersion, liming, deashing and softening operation and pickling chrome tanning process are processed, to remove conventional water-washing step from, also can be washed, and water lotion is collected and entered washing waste liquid pool in order to recycling.
Initial waste liquid used in the present invention comes from respectively traditional main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning process, and the formation situation of various waste liquids is well known by persons skilled in the art.In general, in main immersion waste liquid, contain immersion agent, NaCl, Na
2cO
3, grease-removing agent, grease and degradation production thereof, hair, keratin protein, Saliva Orthana, meat, blood etc., wherein, generally, in waste liquid, residual grease-removing agent content is generally the 15%-30% of initial content, in waste liquid, residual immersion agent content is generally the 15%-25% of initial content, residual Na in waste liquid
2cO
3content is generally the 30%-50% of initial content; In Lime Liquor, contain grease and degradation production thereof, salt, lime, liming agent, S
2-, OH
-, Na
+, Ca
2+, protein and degradation production, enzyme and amine substance etc., wherein, generally, in waste liquid, residual lime is generally the 37%-55% of initial content, residual Na in waste liquid
2s content is generally 2.4g/l-3.2g/l; In deashing and softening waste liquid, contain protein and degradation production thereof, deliming agent, grease-removing agent, grease and degradation production thereof, enzyme and ammonium salt, amine substance etc., wherein in waste liquid, residual enzyme content is generally the 30%-50% of initial content, and in waste liquid, residual amounts of ammonium salt is generally the 30%-40% of initial content; In chroming waste liquor, contain Cr
3+, Cl
-, SO
4 2-, protein and degradation production, grease and degradation production thereof etc., wherein residual Cr in waste liquid
3+be generally 2.8g/1-3.2g/l, Cl
-be generally 7g/l-15g/l, in waste liquid, residual acid group content is generally the 30%-45% of initial content.
Preferably, main immersion, liming and multiple ash process can adopt same rotary drum, at other main immersion, Lime Liquor liquid storage tank and the multiple grey waste liquid liquid storage tank of arranging respectively of rotary drum, in the mode of valve, control rotary drum to the discharging of waste liquid of each liquid storage tank.Specifically, when main immersion, liming and multiple when with a rotary drum, valve 1 is set on rotary drum, for main immersion discharging of waste liquid is arrived to main immersion waste liquid liquid storage tank, meanwhile, valve 2 is set on rotary drum, for Lime Liquor is discharged into Lime Liquor liquid storage tank, meanwhile, valve 3 is set on rotary drum, for answering grey discharging of waste liquid to multiple grey waste liquid liquid storage tank.While discharging main immersion waste liquid, valve 1 is opened, and valve 2,3 is closed, and waste liquid is discharged into main immersion waste liquid liquid storage tank through shunt conduit; During discharge Lime Liquor, valve 2 is opened, and valve 1,3 is closed, and waste liquid is discharged into Lime Liquor liquid storage tank through shunt conduit; During the multiple grey waste liquid of discharge, valve 1,2 is closed, and valve 3 is opened, and waste liquid is discharged into multiple grey waste liquid liquid storage tank through shunt conduit.
Similarly, deashing and softening operation and chrome tanning process also can adopt same rotary drum, on rotary drum side, deashing and softening waste liquid liquid storage tank and chroming waste liquor liquid storage tank are set respectively, in the mode of valve, control rotary drum to the discharging of waste liquid of each liquid storage tank.Specifically, when deashing and softening and chrome tanning are when with a rotary drum, valve 4 is set on rotary drum, be used for deashing and softening discharging of waste liquid to deashing and softening waste liquid liquid storage tank, meanwhile, valve 5 is set on rotary drum, for chroming waste liquor being discharged into chroming waste liquor liquid storage tank.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 through shunt conduit; During discharge chroming waste liquor, valve 4 is closed, and valve 5 is opened, and waste liquid is discharged into chroming waste liquor liquid storage tank through shunt conduit.
In waste liquid cycling and reutilization process of the present invention, for the operation of main immersion, liming, multiple ash, deashing and softening, these the totally-enclosed waste liquid circulations of pickling chrome tanning, should regularly sterilize, regularly detect microorganism, proteolytic enzyme, pH value, chromium ion, calcium ion, sulfide and other relevant composition in waste liquid.Generally, spent lime liquor circulates after more than 100 time, may there is a small amount of useless solid thing, mainly that filter hair process produces, necessary words, can to waste liquid, clean processing by the mode of press filtration, through the isolated solids of press filtration, be used for filling out hole or brickmaking or other purposes, isolated wastewater collection enters spent lime liquor liquid storage tank in order to cycling and reutilization.
The present invention has following beneficial effect:
The present invention has realized in process hides the waste water circulation of each workshop section recycling from raw hide to wet blue, and can unlimitedly circulate, hardly sewage effluent, particularly utilize useless chrome liquor, few 3 ℃-15 ℃ than common process of the moisturizing intensifications in later stage, have saved the energy, and have obtained the blue skin of high-quality.For traditional technology, can save following material: grease-removing agent 15%-30%, immersion agent 15%-25%, soda ash 30%-50%, Na
2s35%-50%, NaHS30%-45%, lime 37%-55%, liming enzyme 20%-40%, liming agent 10%-30%, ammonium sulfate 30%-50%, deliming agent 15%-30%, macerating enzyme 30%-100%, formic acid 30%-45%, sulfuric acid 30%-50%, salt 100%, chromium powder 35%-55%.Certainly concrete technology is different, and the amount of saving material is also slightly different, but in general, can realize and save material 15%-55%, reduces sewage discharge 70%-85%, and wet blue yield of leather increases 1%-3.5%; Shrinkage temperature improves 3 ℃-12 ℃, has obtained high-quality wet blue.The finished product leather property indices of producing thus all reaches requirement, and effectively reduces finished leather loose side rate, has improved the degree of packing of finished leather.In addition, in liming process, the hair being gone out by filter hair machine filter can produce economic benefit, such as processing grease-removing agent, fertilizer etc.
Accompanying drawing explanation
Accompanying drawing 1 is according to the schematic flow sheet of the process for recycling waste leather-making liquid step by step of better effects if of the present invention, notes: the processing of waste liquid can be carried out also can in rotary drum, carrying out in liquid storage tank.
embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the present invention is further described:
Embodiment 1
As shown in Figure 1, in main soaking process, after main immersion waste liquid elimination solid substance, enter main immersion waste liquid liquid storage tank, stir, then by lye pump, extract out and be drained into main soaking drum, the technique of utilizing main immersion waste liquid to carry out main immersion is: with raw hide weighing scale, add 200% main immersion waste liquid, 0.05%ELIPO-S, 0.05% prebiotic precious 3, turn 10 minutes; 0.7% Soaking, 0.3% grease-removing agent, 0.5% soda ash, 0.1% Sodium Sulphide, turn 40 minutes, stops 40 minutes, turns and stop in conjunction with carrying out 3 times, and 0.3% sterilant, turns 20 minutes, spends the night; Turn continuously 40 minutes next day, and main immersion finishes waste water and enters liquid storage tank.
In liming operation, after Lime Liquor elimination solid substance, enter Lime Liquor liquid storage tank, stir, then by lye pump, extract out and be drained into liming rotary drum, utilize Lime Liquor to carry out liming technique to be: with raw hide weighing scale, add 70% Lime Liquor, 0.1%ELIPO-L, turn 10 minutes; 0.2% grease-removing agent, 0.1% Sodium sulfhydrate, turn 30 minutes, stops 5 minutes, turns and stop in conjunction with carrying out 4 times; 70% Lime Liquor, 0.1%ELIPO-L, 0.7% lime, 0.3% sodium sulphite, 0.2% Sodium sulfhydrate, 1.0% liming agent, turn 40 minutes, stops 20 minutes, turns and stop in conjunction with carrying out 2 times; Filter hair 2 hours; 50% Lime Liquor, 0.1%ELIPO-L, 0.3% sodium sulphite, 0.3% sodium hydroxide, 0.15% liming enzyme, 0.6% liming agent, turn 60 minutes, stops 30 minutes, turns and stop in conjunction with carrying out 2 times; Add 20% clear water, 1.5% lime, turn and stop each 30 minutes, then often turn 5 minutes and stop 25 minutes, carry out 2 times, then every rotation stops 90 minutes for 5 minutes, spends the night; In multiple ash process, after multiple grey waste liquid elimination solid substance, enter multiple grey waste liquid liquid storage tank, stir, then by lye pump, extract out and be drained into liming rotary drum, the technique of utilizing multiple grey waste liquid to carry out multiple ash is: with raw hide weighing scale, add 100% multiple grey waste liquid, 0.1%ELIPO-L, turn 10 minutes; 0.8% lime, 0.2%Na
2s (or NaHS), 0.4% liming agent, 0.10% caustic soda, turns 30 minutes, stops 40 minutes, turns 5 minutes and stops 55 minutes (being total to 6 times repeatedly), spends the night or directly goes out drum; Multiple ash finishes rear waste water and enters liquid storage tank, lime-fleshing, split.In deashing and softening operation, after deashing and softening waste liquid elimination solid substance, enter deashing and softening waste liquid liquid storage tank, then by lye pump, extracted out and be drained into deashing and softening rotary drum, the technique of utilizing waste liquid to carry out deashing and softening is: add 100% deashing and softening waste liquid, 0.1%ELIPO-D, turn 10 minutes; 0.2% grease-removing agent, 0.6% deliming agent, 1.2% ammonium sulfate, 0.2% hydrochloric acid, 0.3% acetic acid, turn 40 minutes, and 0.25% macerating enzyme turns 30 minutes.In pickling chrome tanning process, after useless chrome liquor elimination solid substance, be drained into liquid storage tank, with sulfuric acid, adjusting its pH value is 0.6, stir, then by acid proof pump, extract out and flow into chrome tanning rotary drum, the technique of utilizing chroming waste liquor to carry out pickling chrome tanning is: 70% useless chrome liquor, 0.1%ELIPO-D, 0.25% mould inhibitor, turn 10 minutes, 0.6% formic acid (diluting its concentration to 5% left and right with useless chrome liquor), turn 20 minutes, 0.6% sulfuric acid (diluting its concentration to 5% left and right with useless chrome liquor), divides three times equally and adds, at interval of interpolation in 10 minutes once, turn 90 minutes; 0.2% fatting agent, rotates 30 minutes, stops 1.5 hours; 2.0% chromium powder, turns 30 minutes, and 2% chromium powder turns 1 hour; 0.5% sodium formiate, turns 30 minutes; 0.25% carries alkaline agent, turns 4 hours, after be warming up to 35 ℃, add 50% useless chrome liquor, 0.1%ELIPO-D, turn 3 hours.
The shrinkage temperature that records wet blue is 105 ℃, and wet blue color is turquoise, and grain is careful.
In the situation that not departing from spirit of the present invention or substantive features, can implement the present invention with other form, with reference to claim but not above-mentioned specification sheets, as indication scope of the present invention.
Claims (15)
1. the process for recycling waste leather-making liquid step by step of a better effects if, it is characterized in that proceed step by step waste liquid cycling and reutilization in main immersion, liming, multiple ash, deashing and softening, pickling chrome tanning process, the waste liquid that each operation produces adds certain special preparation, add-on is 0.05%-0.3% (take waste liquid amount as radix), and above-mentioned operation all realizes closed circulating.Comprise the steps:
(1) the waste liquid cycling and reutilization of main soaking process: main immersion waste liquid liquid storage tank is set on main soaking drum side, in the waste liquid elimination waste liquid of next autonomous soaking process, after solid substance, enter main immersion waste liquid liquid storage tank, stir, to be ready for use on down the main immersion of batch skin; The technique of utilizing main immersion waste liquid to carry out main immersion is: with raw hide weighing scale, add the main immersion waste liquid of 70%-250%, 0.05%-0.3% special preparation, turn 5-15 minute; 0.1%-1.0% Soaking, 0.1%-0.8% grease-removing agent, 0.1%-1.0% soda ash, 0.05%-0.3% Sodium Sulphide, turn 30-80 minute, stops 10-50 minute, turns and stop in conjunction with carrying out 1-4 time; 0.1%-0.4% sterilant, turns 5-20 minute, spends the night; Turn continuously 10-50 minute next day, main immersion finishes waste water and enters liquid storage tank.Should regularly detect the microbe population in waste liquid, general every circulation detects once for two to three times.
(2) the waste liquid cycling and reutilization of liming operation: on liming rotary drum side, Lime Liquor liquid storage tank is set, from entering Lime Liquor liquid storage tank after solid substance in the Lime Liquor elimination waste liquid of liming operation, stirs, to be ready for use on down the liming of batch skin; The technique of utilizing Lime Liquor to carry out liming is: with raw hide weighing scale, add 20%-90% Lime Liquor, 0.05%-0.3% special preparation, turn 5-15 minute; 0.15%-0.3% grease-removing agent, 0.1%-0.5% Sodium sulfhydrate, turn 10-40 minute, stops 5-15 minute, turns and stop in conjunction with carrying out 3-6 time; 30%-90% Lime Liquor, 0.05%-0.3% special preparation, 0.2%-1.0% lime, 0.2%-0.6% sodium sulphite, 0.2%-0.5% Sodium sulfhydrate, 0.3%-1. 5% liming agent, turn 10-50 minute, stops 5-30 minute, turns and stop in conjunction with carrying out 1-3 time; Filter hair 1-3 hour; 20%-60% Lime Liquor, 0.05%-0.3% special preparation, 0.2%-1.0% sodium sulphite, 0.05%-0.4% sodium hydroxide, 0.1%-0.8% liming agent, turn 30-90 minute, stops 10-40 minute, turns and stop in conjunction with carrying out 2-4 time; Add 10%-20% clear water, 0. 5%-2.0% lime, turn and stop each 10-40 minute, then often turn 5-10 minute and stop 20-40 minute, carry out 2-4 time, then often turn 5-10 minute and stop 30-120 minute, spend the night; Before each use, all need to chemically examine Sodium Sulphide in spent lime liquor, Ca
2+equal size.In liming process, depending on the hair root degree that comes off, utilize in time filter hair machine filter hair;
(3) the waste liquid cycling and reutilization of multiple ash process: multiple grey waste liquid liquid storage tank is set multiple grey rotary drum is other, comes to enter multiple grey waste liquid liquid storage tank 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 criticizing skin; The technique of utilizing multiple grey waste liquid to carry out multiple ash is: with raw hide weighing scale, add the multiple grey waste liquid of 70%-220%, 0.05%-0.3% special preparation, turn 5-15 minute; 0.2%-1.5% lime, 0.05%-1.0%Na
2s (or NaHS), 0.1%-0.7% liming agent, 0.05%-0.3% caustic soda, turned about 30 minutes, stops 30-60 minute, turns 5-20 minute and stop 30-60 minute (being total to 3-8 time repeatedly), spends the night or directly go out drum; Multiple ash finishes rear waste water and enters liquid storage tank, lime-fleshing, split;
(4) the waste liquid cycling and reutilization of deashing and softening operation: at the other deashing and softening waste liquid liquid storage tank that arranges of deashing and softening rotary drum, from entering deashing and softening waste liquid liquid storage tank after solid substance in 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 of utilizing deashing and softening waste liquid to carry out deashing and softening is: with graywall weighing scale, add 30%-220% deashing and softening waste liquid, 0.05%-0.3% special preparation, turn 5-15 minute; 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, turn 15-60 minute; 0%-0.3% macerating enzyme, turns 15-40 minute.Deashing and softening finishes rear waste water and enters liquid storage tank.Every circulation primary all should detect proteolytic enzyme and the microbe population in waste liquid, and proteolytic enzyme detects and preferably uses LC-MS instrument, also can use photoelectric colorimetry, according to detected result, determines the macerating enzyme quantity that should add and whether needs to add sanitas;
(5) the waste liquid cycling and reutilization of pickling chrome tanning process: on pickling chrome tanning rotary drum side, chroming waste liquor liquid storage tank is set, this pond is preferably deep to underground 2-8 rice in order to temperature control, and preferably has standby pool.From entering chroming waste liquor liquid storage tank after solid substance in the waste liquid elimination waste liquid of chrome tanning process, after cooling, with acid, regulate the pH value of chroming waste liquor to 0.2-1.2, stir, to be ready for use on down the pickling chrome tanning of batch skin.The technique of utilizing chroming waste liquor to carry out pickling chrome tanning is: with graywall weighing scale, add 20%-100% chroming waste liquor, 0.05%-0.3% special preparation, 0.1%-0.4% mould inhibitor, 0%-5% salt or other material that has inhibition acid to swell and act on, turn 5-30 minute; 0.3%-0.6% formic acid, turns 10-40 minute; 0.2%-0.7% sulfuric acid, divides two to four times equally and adds, and every minor tick 5-30 minute, turns 70-100 minute; 0%-0.5% fatting agent, turns 15-50 minute, stops 1-2 hour; 0.5%-3.0% chromium powder, turns 20-60 minute; 0.5%-3.0% chromium powder, turns 0.5-2.0 hour; 0.1%-0.7% sodium formiate, turns 15-55 minute; 0.15%-0.45% carries alkaline agent, turns 2.0-5.5 hour; Add 20%-80% chroming waste liquor, 0.05%-0.3% special preparation, turn 5-15 minute; After be warming up to 28 ℃-38 ℃, turn 2-5 hour.Should regularly chemically examine chromium content and pH value in useless chrome liquor.Should regularly detect the microbe population in waste liquid, generally circulate and detect once for three to five times, mainly detect mould quantity, according to detected result, determine the consumption of mould inhibitor.
2. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, it is characterized in that the waste liquid that each operation produces adds certain special preparation, as prebiotic precious series product: ELIPO-S, ELIPO-L, ELIPO-D, prebiotic precious 3, be conducive to waste liquid circulation.These special preparations are grouped into by one-tenth such as vitriol, carbonate, silicate, acetate, proteolytic enzyme, amino acid.
3. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, is characterized in that the hair that filter hair machine filter goes out, and can produce economic benefit, such as producing grease-removing agent, fertilizer etc.
4. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, it is characterized in that Lime Liquor circulates after more than 100 time, may there is a small amount of useless solid thing, mainly that filter hair process produces, necessary words, can to waste liquid, clean processing by the mode of press filtration, through the isolated solids of press filtration, be used for filling out hole or brickmaking or other purposes, isolated wastewater collection enters Lime Liquor liquid storage tank in order to cycling and reutilization.
5. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, is characterized in that each liquid storage tank is provided with whipping appts, also can carry out hand mixing.
6. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, the waste collection that its feature produces in lime-fleshing and split process enters liming or multiple grey waste liquid liquid storage tank in order to cycling and reutilization.
7. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, it is characterized in that main immersion, liming and multiple ash process can adopt same rotary drum, at other main immersion waste liquid liquid storage tank, Lime Liquor liquid storage tank and the multiple grey waste liquid liquid storage tank of arranging respectively of rotary drum, with mode or other shunting mode of valve, control rotary drum to the discharging of waste liquid of each liquid storage tank.
8. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, it is characterized in that deashing and softening operation and chrome tanning process adopt same rotary drum, at other deashing and softening waste liquid liquid storage tank and the chroming waste liquor liquid storage tank of arranging respectively of rotary drum, with mode or other shunting mode of valve, control rotary drum to the discharging of waste liquid of each liquid storage tank.
9. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, is characterized in that the skin after liming, deashing and softening and chrome tanning process are processed is removed conventional water-washing step from.Also can wash, and washing waste liquid is carried out to cycling and reutilization.When the washing waste liquid of recycle graywall, should add acid that its pH value is adjusted between 6-10.
10. the process for recycling waste leather-making liquid step by step of better effects if as claimed in claim 1, is characterized in that at the other standby pool that arranges again of chroming waste liquor liquid storage tank.Other operation also can arrange standby pool as liming and deashing and softening operation etc.
The process for recycling waste leather-making liquid step by step of 11. better effects if as claimed in claim 1, is characterized in that consumption, heating and cooling amplitude, operating time and the operation steps of various chemical materials all can be made significantly adjustment.
The process for recycling waste leather-making liquid step by step of 12. better effects if as claimed in claim 1, it is characterized in that the wherein waste liquid cycling and reutilization technique of any procedure, comprise that main immersion, liming, multiple ash, deashing and softening, pickling, tanning etc. all can be combined with separately or with other operation.
The process for recycling waste leather-making liquid step by step of 13. better effects if as claimed in claim 1, is characterized in that in liming process, depending on the hair root degree that comes off, utilizes in time filter hair machine filter hair.While being goatskin, lamb skin and pigskin as doing raw hide, the removal of most of hair is carried out drum is outer, and last part Mao Yike is used and filters a mao machine filter and go out in liming process.
The process for recycling waste leather-making liquid step by step of 14. better effects if as claimed in claim 1, is characterized in that in pickling Chrome Tanning Process, the add-on of salt is 0, also can add a small amount of salt or other material that has inhibition acid to swell and act on.
The process for recycling waste leather-making liquid step by step of 15. better effects if as claimed in claim 1, the total consumption that it is characterized in that chromium powder is 2.5%-5.5%.
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| CN201310134541.9A CN103525955A (en) | 2013-04-18 | 2013-04-18 | Tanning waste liquor stepwise recycling process with good effects |
| PCT/CN2013/083514 WO2014169564A1 (en) | 2013-04-18 | 2013-09-13 | Tannery waste liquid step-by-step recycling process having improved effect |
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| CN201310134541.9A CN103525955A (en) | 2013-04-18 | 2013-04-18 | Tanning waste liquor stepwise recycling process with good effects |
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| MX2017015798A (en) * | 2015-06-09 | 2018-06-13 | Proklean Tech Pvt Ltd | Probiotic composition as leather auxiliary agents and use thereof. |
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| WO2014169564A1 (en) | 2014-10-23 |
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