CN103773906B - Integrated water saving method for leather-making - Google Patents
Integrated water saving method for leather-making Download PDFInfo
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Abstract
An integrated water saving method for leather-making, is characterized in that, comprises step (1) and washes skin fast: inserted by wet-salted bovine hide in the body lotion in overloading drum and carry out, and is interrupted running; (2) main immersion, depilation, liming three operation merge, and carry out with bath; (3) carry out washing step after cuing open graywall operation, washing step adopts vexed washing; (4) deliming, softening two operations merge, and carry out with bath; (5) pickling, tanning processes merge, and carry out with bath; (6) retanning, neutralize two operations merge, with bath carry out; (7) filling, dyeing, stuffing three operation merge, and carry out with bath; (8) wash, adopt vexed washing.After the invention process, overall water saving, emission reduction effect are: water of productive use amount reduction 40 ~ 50%, COD CER is 30%, chromium CER 90%, basicity CER 60%.Of the present inventionly clean characteristic and environmental protection characteristic is further enhanced.
Description
Technical field
The present invention relates to a kind of integrated water saving method for leather-making, belong to and clean leather manufacture technical field, is the utilisation technology in leather process for processing.
Background technology
Curriery is the industry that raw material carries out deep processing based on the by product of livestock industry, that various different animal hides is through physics, chemical process processings such as depilation, tannings, again through the process for processing operation such as covering with paint, arrangement, produce the process of manufacture of various leather products with softness, the performance such as plentiful, ventilative.
The processing of the operations such as the preparation of process hides, tanning and rear wet ornamenting take water as the production process of medium, and by physics, chemistry and mechanical workout effect, final production goes out the resultant Leather that various different-style and quality product require.Traditional tanning production often processes 1 ton of wet salted hide needs consumption fresh water amount to be about 50 ~ 60 tons (existing tanning production technique is shown in Fig. 1), consume various chemical and be about 450 ~ 550 kilograms, discharge simultaneously about 45 ~ 55 tons containing various pollutent (wherein: COD180 ~ 220kg ±, SS125kg ± etc.) waste water, and containing chromium, not containing the solid waste of chromium.Traditional tanning production not only wastes a large amount of water resourcess and various chemical materials, also brings serious potential harm to environment protection simultaneously.
Summary of the invention
The object of the invention is the deficiency needing to consume a large amount of fresh waters (comprise process water and wash Pi Yongshui) for existing tanning technology in process of production, a kind of that clean, integrated process hides water-saving technology method is provided, by the integrated water-saving technique adoption of tanning production whole process, and correspondingly Technology adjusts and balance, realize the integrated water-saving technology method of tanning production whole process, effectively reduce the consumption of the water of tanning production and the quantity discharged of waste water, reduce the discharge of various pollutent in waste water simultaneously, improve the quality product of resultant Leather.
In order to reach the object of the integrated water saving of leather-making technology and pollution reduction, technical scheme of the present invention is:
1, the preparation of tanning production and tanning processes all carry out in overloading drum, and the rear wet ornamenting operations such as retanning, dyeing, stuffing are all carried out, to realize integrated water saving and the reduction of discharging of leather making process in Y type rotary drum.
2, skin operation in Shen adopts the mode being aided with chemical and auxiliary enzymes preparation to improve the backwater effect of rawhide, substitutes the operation of pre-soaking process.
3, existing main immersion, depilation, liming operation adopt and carry out with bath, and immersion adopts defatting enzyme; Depilation, the depilation of liming employing guarantor hair substitute and ruin cant method.
4, retain and existingly cut open the washing step after graywall, and change vexed washing twice.
5, merge deliming, softening process, deliming adopts without ammonium salt deliming technology, softening employing enzyme bating technology.
6, cancel existing washing, directly pickling after changing bath, tanning adopt little liquor ratio, high-absorption chrome tanning technique, the tanning later stage adds acrylic crosslinking agent and improves chrome uptake.
7, retanning adopts and adopts weak base agent and dispersion agent to substitute ammonium salt without chromium retanning agent, neutralization, and dyeing, stuffing adopt high-selenium corn staining agent and fatting agent to improve upper dye and the stuffing effect of dyestuff, adopt twice vexed water washing after dyeing, stuffing.
Adopt after such scheme, the present invention compared with prior art, the technical superiority had:
One, all adopt overloading drum and Y type rotary drum to implement tanning production, Automation of Manufacturing Process degree significantly improves, and water consumption controls to add more accurate with various chemical.
Two, the merging of part producing operation, and only retain deliming in production process, softening before washing and dyeing, washing after stuffing, realize the integrated water saving of technological process, water-saving result reaches 40 ~ 50%.
Three, low-sulfur Fa Baomao depilation liming, use part Sodium sulfhydrate and depilation zymin to substitute the use of sodium sulphite, the discharge of hair removal wastewater medium sulphide content reduces by 70%, COD and discharges minimizing 50%.
Four, use deliming without ammonium agent to carry out deliming, soften, in deliming, softening waste water, the discharge of inorganic ammonia nitrogen reduces more than 90%.
Five, little liquor ratio pickling, tanning, adopt the tanning later stage to add chromium cross linker and improve chrome uptake rate, and the tanning later stage completes tanning operations by the automatic heating that suitably raising rotary drum rotating speed realizes in tanning later stage rotary drum, after tanning, in waste water, the discharge of chromium reduces 90%, COD discharge minimizing 30%.
After the technology of the present invention is implemented, overall water saving, emission reduction effect are: water of productive use amount reduction 40 ~ 50%, COD CER is 30%, chromium CER 90%, basicity CER 60%.Of the present inventionly clean characteristic and environmental protection characteristic is further enhanced.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of prior art;
Fig. 2 is process flow sheet of the present invention.
Embodiment
Present invention is disclosed a kind of integrated water saving method for leather-making, be the improvement to existing production method, concrete technology flow process is shown in Fig. 2.
Main processes of the present invention is described as follows (in Fig. 2, some normal process steps repeats no more):
1) skin is washed fast:
Carry out in overloading drum, rotary drum rotating speed: 2 ~ 4rpm.
Get wet-salted bovine hide 100 parts, add 200 parts of fresh waters, 0.05 ~ 0.2 part of Soaking A (Lang Sheng LANXESS company, name of product: CISMOLLANSA-C, for non-ionic polymers or nonionogenic tenside), 0.02 ~ 0.2 part of soaking enzyme (De Rui TFL company, name of product: PELLVITC, be made up of hydrolysising protease and activator), 0.05 ~ 0.2 part of sterilant (Shanghai Jia Yi company, name of product: 1140 are organic sulfide).Temperature 20 ~ 25 DEG C.Rotate 30 minutes, stop 30 minutes, adopt soda to regulate body lotion final ph about 10,4 ~ 6 hours total times.
2) main immersion, depilation, liming:
Carry out in overloading drum, rotary drum rotating speed: 2 ~ 4rpm.
Get and to wash fast after skin and fleshing fur 100 parts, add 150 ~ 200 parts of water, temperature 20 ~ 25 DEG C, add 0 ~ 0.2 part of Soaking A, 0 ~ 0.3 part of soaking enzyme, 0.05 ~ 0.3 part of sterilant, 0 ~ 0.3 part of grease-removing agent C (Lang Sheng LANXESS company, name of product: BAYMOLADN-C, for multiple nonionogenic tenside and anion surfactant are composited), rotate 30 ~ 60 minutes, rotation per hour 20 ~ 40 minutes totally 2 ~ 3 times again, rotation per hour 10 minutes, main immersion 10 ~ 16 hours altogether.Check the state of Baume, temperature, PH and fur.
The sterilant content added in main soaking process, avoids occurring the rear rotten pore phenomenon of depilation.
With bathing depilation, liming: add 0.6 ~ 1.2 part of auxiliary liming agent D (You Ni Chemical Engineering Technology company limited, name of product: KSU, the mixture for Ammonia condensing agent and natural reduzate) again, rotate 30 minutes; Add 0.8 ~ 1.2 part of lime again, rotate 20 ~ 40 minutes, stop 40 ~ 20 minutes; Add 0.6 ~ 1.2 part of Sodium sulfhydrate again to rotate 20 ~ 60 minutes, lose hair or feathers; Add 0.2 ~ 0.5 part of auxiliary liming agent E (Lang Sheng LANXESS company again, name of product: CISMOLLAN4008-C, containing enzyme non-organic amine environment-friendly type auxiliary liming agent), 0.2 ~ 0.5 part of sodium sulphite, 0.3 ~ 0.8 part of lime, rotate 10 ~ 30 minutes, stop repeating twice altogether in 20 ~ 40 minutes; 0.2 ~ 0.5 part of sodium sulphite, 0.3 ~ 0.8 part of lime, rotate 10 ~ 30 minutes again, stops repeating twice altogether in 20 ~ 40 minutes; Add 0.8 ~ 1.5 part of lime again and turn 15 minutes, then often turn 5 minutes and stop 55 minutes, 20 ~ 24 hours liming total times.Finally go out drum, fleshing, split, weigh, prepare to carry out deashing and softening operation.
3) retain the washing step after cuing open graywall, change vexed washing twice into.
4) deliming, softening:
Carry out in tanning drum, rotary drum rotating speed: 6 ~ 8rpm.
Get the head layer graywall after 100 parts of splits, washing temperature adjustment, 150 ~ 200 parts of water, interior temperature 30 ~ 33 DEG C, turn 10 minutes discharge section water, stay 60 ~ 100 parts, water add again 0.8 ~ 1.2 part of deliming auxiliary agent F (Sheng Hui company, name of product: Sheng Li can JNU, the mixture of unazotized organic acid and salt), rotate 30 ~ 50 minutes; Add 0.3 part of macerating enzyme G (De Rui TFL company, name of product: OROPONOR, is made up of pancreatin) again with bath, rotate 30 ~ 60 minutes, draining.
5) pickling, tanning:
Carry out in tanning drum, rotary drum rotating speed: 6 ~ 8rpm.
100 parts, ox-hide after softening above getting, adds 30 parts of normal-temperature water, 5 portions of salt, rotates and surveys Baume 5 ~ 5.5 in 15 minutes; Add 1.0 parts of auxiliary pickling agent A (De Rui TFL company, name of product: SELLATANPA, gathers sulfonic acid by modification and form) again, rotate 30 ~ 60 minutes; Add 0.3 ~ 0.6 part of sulfuric acid again, rotate 30 ~ 60 minutes; Add 0.5 ~ 1.0 part of sodium formiate again, rotate 10 minutes; Add 5 parts of chromium powders again, rotate 120 minutes; (that chemical company of DESAY, name of product: DESOTANAR, containing methacrylic acid salt material to add chromium cross linker B again.), rotate 60 minutes; Add 0.2-0.4 part again and carry alkaline agent (Tang Pule company, name of product: TRUPOTANMON, is made up of magnesium oxide), rotate 6 ~ 8 hours.End temp 38 ~ 42 DEG C.
6) retanning, neutralization:
Carry out in retanning Y type rotary drum, rotary drum rotates: 6 ~ 8rpm.
Get the blue skin 100 parts after shaving, add the water of 200 parts, temperature 40 ~ 45 DEG C, add 0.1 ~ 0.3 part of grease-removing agent (Lang Sheng LANXESS company, name of product: BAYMOLADN-C, for multiple nonionogenic tenside and anion surfactant are composited), 0.2 ~ 0.5 formic acid, rotate 30 ~ 60 minutes, draining; Add the water of 100 parts of temperature 35 DEG C again, 1 ~ 4 part of synthesis aluminium tannin tanning agent (BASF AG, name of product: BasyntanAS, for sulfone aluminum tanning agent), 0.5 ~ 2.0 part of alkanoic, 0.5 ~ 1.0 part of acidproof oil (Tang Pule company, name of product: TruponPEM, for synthetic phosphoric acid ester), rotate 30 ~ 60 minutes; Add 1.0 ~ 2.0 parts of sodium formiates again, rotate after 60 ~ 90 minutes, then add in 1.0 ~ 2.0 parts and tannin (Lang Sheng LANXESS company, name of product: TANIGANPAK-S, displacement tannin containing phenolic), 1.0 ~ 2.0 parts of sodium formiates, rotate 40 ~ 60 minutes, draining.
7) filling, dyeing, stuffing:
Carry out in retanning Y type rotary drum, rotary drum rotates: 6 ~ 8rpm.
Add 80 parts of fresh waters, temperature 30 DEG C, add 4 ~ 6 parts of acrylate resin tanning agents, rotate 30 minutes; Add 1 ~ 3 part of auxiliary syntan (Sheng Hui company, name of product: JAN, the both sexes tannin of aromatic sulphonic acid and name of product: JHL, the mixture by aromatic sulphonate condenses, amino-complex and additive) again and rotate 20 minutes; Add 2 ~ 4 parts of aminoresin, 2 ~ 4 parts of vegetable tanning agent (Atlantic Ocean, Wenzhou companies again, name of product: quebracho extract ATO, Mimosa tannin extract), 2 ~ 4 parts of dicyandiamide resins, 2 ~ 4 parts of melamine resins, 2 ~ 4 parts of dyestuffs, turn 60 ~ 120 minutes; Add 2 ~ 4 parts of electrolyte-resistant synthetic oils (Tang Pule company, name of product: TruponOSL, sulphiting/phosphoric acid salt triglyceride oil again; Name of product: TruponDB, sulfation/phosphoric acid salt Witepsol W-S 55), 2 ~ 4 parts of lanolin, 2 ~ 4 parts become neat's foot oils, rotate 60 ~ 90 minutes; Add 1 ~ 3 part of formic acid again, rotate 10 ~ 20 minutes continuously, go out drum, enter finishing process.
8) washing step is retained, vexed washing twice.
The material number related in the present invention is weight fraction.
Significantly reduce water consumption by this technology, water-saving result is obvious.Adopt through preferred chemical materials and adjusting process technology, the blue cortex amount produced is protected, and the blue skin difference of normally producing with our factory is very little.Retanning dyeing and fat-liquoring, with bath, selects tanning agent and the fatting agent of some electrolyte-resistants, ensures to absorb completely, the scytoblastema consolidation produced like this, plentiful, flexible, can reach the requirement of upper leather completely.And significantly save process hides water, meeting the modern times cleans process specifications.
Object of the present invention realizes integrated water saving and pollution reduction by following technology point:
The technique effect of important procedure of the present invention is described as follows:
1, strengthen the backwater of raw hide and return fresh effect:
In the quick Shen skin and main immersion process of raw hide, use Soaking, soaking enzyme and sterilant continuously, ensure the abundant backwater of rawhide and return fresh.Soaking effectively can dissolve the dirt on raw hide surface and have the effect of good emulsifying grease, therefore can accelerate immersion; Soaking enzyme can make pelt surface more clean, and fine, soft fur, hair root more easily remove; Sterilant can suppress microorganism growth strongly, effectively, kill bacteria, and protection raw hide escapes injury when washing skin and main immersion.
2, the solvability of depilation, limiting material is strengthened:
The auxiliary liming agent D used in depilation, liming process and auxiliary liming agent E has the dissolving function promoting sulphur compound and lime in depilation, liming liquid, make depilation, liming mixed solution is in the suspension mixed completely all the time, avoid the equilibrium problem because cannot keep system chemical material in depilation, liming process because of the consumption of mixed solution local material.
3, little liquor ratio pickling, tanning:
After tanning, final liquor ratio reduces about 1/2 relative to prior art, discharge discharge reduction about 1/2, reason for add many other materials in pickling, tannery, and these material major parts need to dissolve or add after dilution, therefore the more conventional minimizing of liquor ratio at the end of pickling, tanning system.The tanning later stage leans on the mechanical effect of rotary drum and wet blue to realize the intensification in tanning later stage; The use of Acrylates material substantially increases the combination of chromium at collagen carboxyl, carries simultaneously and makes each fixing more firm on collagen carboxyl adding of alkaline agent.4, degreasing effect is strengthened:
During main immersion and retanning, carry out the fat abstraction of rawhide and wet blue, make finished leather more soft on the one hand; Make on the other hand resultant Leather can not because degreasing is clean with the taste of rawhide.
5, retanning fully and filling effect
Use multiple retanning agent (retanning procedures), weighting agent carries out sufficient retanning and filling, make resultant Leather more plentiful.
Claims (7)
1. an integrated water saving method for leather-making, is characterized in that, this inventive method comprises the following steps:
(1) wash skin fast: inserted by wet-salted bovine hide in the body lotion in overloading drum and carry out, be interrupted running;
(2) main immersion, depilation, liming three operation merge, and carry out with bath;
(3) carry out washing step after cuing open graywall operation, washing step adopts vexed washing;
(4) deliming, softening two operations merge, and carry out with bath;
(5) pickling, tanning processes merge, and carry out with bath;
(6) retanning, neutralize two operations merge, with bath carry out;
(7) filling, dyeing, stuffing three operation merge, and carry out with bath;
(8) wash, adopt vexed washing;
Rotating speed 2 ~ the 4rpm of described step (1) overloading drum; Described body lotion is: get wet-salted bovine hide 100 parts, adds 200 parts of fresh waters, 0.05 ~ 0.2 part of Soaking A, 0.02 ~ 0.2 part of soaking enzyme, 0.05 ~ 0.2 part of sterilant; Bath temperature 20 ~ 25 DEG C; Turn and stop combining, adopt soda to regulate body lotion final ph to be 10, total duration 4 ~ 6 hours; Described Soaking A is the product of Lang Sheng LANXESS company, and name of product is: CISMOLLANSA-C.
2. integrated water saving method for leather-making according to claim 1, is characterized in that, the main immersion in described step (2), depilation, liming three operations are carried out in overloading drum, rotary drum rotating speed: 2 ~ 4rpm; This main soaking process process is: get fur 100 parts after pre-immersion fleshing, add the water of 150 ~ 200 parts of temperature 20 ~ 25 DEG C, 0 ~ 0.2 part of Soaking A, 0 ~ 0.3 part of soaking enzyme, 0.05 ~ 0.3 part of sterilant, 0 ~ 0.3 part of grease-removing agent C, turn and stop combining, main immersion duration is 10 ~ 16 hours; Depilation operation be followed successively by immunity protect hair, hair root loosen, depilation, solid-liquid separation and depilatory solution circulation; Liming realizes by mending ash in bath; The pH value of final body lotion is 11.0 ~ 11.5; Described grease-removing agent C is the product of Lang Sheng LANXESS company, and name of product is: BAYMOLADN-C.
3. integrated water saving method for leather-making according to claim 2, is characterized in that, the depilation in described step (2) and the technological process of liming are: after main soaking process, then add 0.6 ~ 1.2 part of auxiliary liming agent D, rotate 30 minutes; Add 0.8 ~ 1.2 part of lime again, rotate 20 ~ 40 minutes, stop 40 ~ 20 minutes; Add 0.6 ~ 1.2 part of Sodium sulfhydrate again to rotate 20 ~ 60 minutes, lose hair or feathers; Add 0.2 ~ 0.5 part of auxiliary liming agent E, 0.2 ~ 0.5 part of sodium sulphite, 0.3 ~ 0.8 part of lime again, rotate 10 ~ 30 minutes, stop repeating twice altogether in 20 ~ 40 minutes; Add 0.2 ~ 0.5 part of sodium sulphite, 0.3 ~ 0.8 part of lime again, rotate 10 ~ 30 minutes, stop repeating twice altogether in 20 ~ 40 minutes; Add 0.8 ~ 1.5 part of lime again and turn 15 minutes, then often turn 5 minutes and stop 55 minutes, 20 ~ 24 hours liming total times; Described auxiliary liming agent D is the product of You Ni Chemical Engineering Technology company limited, and name of product is: KSU; Described auxiliary liming agent E is the product of Lang Sheng LANXESS company, and name of product is: CISMOLLAN4008-C.
4. integrated water saving method for leather-making according to claim 1, it is characterized in that, described step (4) deliming and softening process carry out in tanning drum, rotary drum rotating speed: 6 ~ 8rpm, get the head layer graywall after 100 parts of splits, washing temperature adjustment, 150 ~ 200 parts of water, interior temperature 30 ~ 33 DEG C, turns 10 minutes discharge section water, stay 60 ~ 100 parts, water to add 0.8 ~ 1.2 part of deliming auxiliary agent F again, rotate 30 ~ 50 minutes; Add 0.3 part of macerating enzyme G again with bath, rotate draining after 30 ~ 60 minutes; Described deliming auxiliary agent F is the product of Sheng Hui company, and name of product: Sheng Li can JNU; Described macerating enzyme G is the product of De Rui TFL company, name of product: OROPONOR.
5. integrated water saving method for leather-making according to claim 1, is characterized in that, described step (5) pickling and tanning processes carry out in tanning drum, rotary drum rotating speed: 6 ~ 8rpm; Get 100 parts, ox-hide after softening, add 30 parts of normal-temperature water, 5 portions of salt, rotate and survey Baume 5 ~ 5.5 in 15 minutes; Add 1.0 parts of auxiliary pickling agent A again, rotate 30 ~ 60 minutes; Add 0.3 ~ 0.6 part of sulfuric acid again, rotate 30 ~ 60 minutes; Add 0.5 ~ 1.0 part of sodium formiate again, rotate 10 minutes; Add 5 parts of chromium powders again, rotate 120 minutes; Add chromium cross linker B again, rotate 60 minutes; Add 0.2-0.4 part again and carry alkaline agent, rotate 6 ~ 8 hours, end temp 38 ~ 42 DEG C; Described chromium cross linker B is the product of your chemical company of DESAY, name of product: DESOTANAR.
6. integrated water saving method for leather-making according to claim 1, is characterized in that, described step (6) retanning, neutralizes two operations and carries out in retanning Y type rotary drum, rotary drum rotating speed: 6 ~ 8rpm; Get the blue skin 100 parts after shaving, add the water of 200 parts of temperature 40 ~ 45 DEG C, add 0.1 ~ 0.3 part of grease-removing agent, 0.2 ~ 0.5 part of formic acid, rotate draining after 30 ~ 60 minutes; Add the water of 100 parts of temperature 35 DEG C again, 1 ~ 4 part of synthesis aluminium tannin tanning agent, 0.5 ~ 2.0 part of alkanoic, 0.5 ~ 1.0 part of acidproof oil, rotate 30 ~ 60 minutes; Add 1.0 ~ 2.0 parts of sodium formiates again, rotate after 60 ~ 90 minutes, then add in 1.0 ~ 2.0 parts and tannin, 1.0 ~ 2.0 parts of sodium formiates, rotate draining after 40 ~ 60 minutes.
7. integrated water saving method for leather-making according to claim 1, is characterized in that, described step (7) filling, dyeing, stuffing three operations are carried out in retanning Y type rotary drum, rotary drum rotating speed 6 ~ 8rpm;
Add the water of 80 parts of temperature 30 DEG C, add 4 ~ 6 parts of acrylate resin tanning agents, rotate 30 minutes; Add 1 ~ 3 part of auxiliary syntan again and rotate 20 minutes; Add 2 ~ 4 parts of aminoresin, 2 ~ 4 parts of vegetable tanning agents, 2 ~ 4 parts of dicyandiamide resins, 2 ~ 4 parts of melamine resins, 2 ~ 4 parts of dyestuffs again, rotate 1-2 hour; Add 2 ~ 4 parts of electrolyte-resistant synthetic oils, 2 ~ 4 parts of lanolin, 2 ~ 4 parts of one-tenth neat's foot oils again, rotate 60 ~ 90 minutes; Add 1 ~ 3 part of formic acid again.
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| CN106755625A (en) * | 2015-11-25 | 2017-05-31 | 张壮斗 | The technology of skin is done using waste liquid |
| CN106834556B (en) * | 2016-12-30 | 2019-09-17 | 兴业皮革科技股份有限公司 | A kind of same bath process of hygrometric state dyeing and finishing towards cattle hide upper leather |
| CN113122662B (en) * | 2021-05-28 | 2022-06-21 | 齐鲁工业大学 | Integrated unhairing method without liquid change for compound enzyme preparation |
| CN113278744B (en) * | 2021-06-05 | 2022-04-01 | 百草边大生物科技(青岛)有限公司 | Preparation method of cow leather containing bioactive components |
| CN113528717A (en) * | 2021-07-14 | 2021-10-22 | 台山市广一皮业有限公司 | Pickling and tanning integrated process for leather production and processing |
| CN114277202A (en) * | 2021-11-12 | 2022-04-05 | 宁夏西部皮草有限公司 | Production and processing technology of high-density shorn sheepskin |
| CN114921596B (en) * | 2022-05-13 | 2023-12-22 | 河南中牛实业有限公司 | Production method of environment-friendly Italian style cowhide sofa leather |
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