CN101265506B - Ashless and alkali sulfide free depilation liming treatment method for preparing leather from goatskin - Google Patents
Ashless and alkali sulfide free depilation liming treatment method for preparing leather from goatskin Download PDFInfo
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Abstract
The invention relates to a goatskin currying processing method of alkali depilation liming without dust and vulcanization. The method is characterized in that sodium sulfide, sodium bisulfide and lime are not used; lime precipitate and residua do not appear to ensure the drained waste water to be more easily processed. The pollution to the environment in the currying process is greatly reduced. The washing dust skin which is a highest water cost working procedure is eliminated, and the saved water is about 20 percent to 40 percent of the total draining quantity of waster water. The damage to finished leather quality caused by mechanical effect is reduced; the loose surface rate caused by mechanical effect is greatly reduced; the production period is also shortened; various materials are saved and the production combined cost is reduced.
Description
Technical field
The present invention relates to a kind of ashless, alkali sulfide free depilation liming treatment method of preparing leather from goatskin, belong to process hides and prepare the workshop section field.Depilation liming was handled before this method was applicable to the tanning of goat leather for making garment, glove leather, upper leather of demand on the current market.
Technical background
Over more than 20 year, the tanning industry of China has played immeasurable effect for the city commodity market of exporting goods and earning foreign currency, enrich, development pastoral area, rural area economy.Yet the leather industry development is restricted because of the blowdown problem again.At present, the pressure of environment protection has become the trend of closing down or carrying out the regional transfer of leather industry.
At present, 98% above tannery uses Sodium Sulphide lime tradition process hides depilation liming technology, and its advantage is that expense is low, quick, depilation is clean, can adapt to the production of various leathers; But it is big that its shortcoming is a material usage, and COD, BOD, TSS value and sulfide content are very high in the waste liquid, and the waste liquid post precipitation produces a lot of mud, and difficult treatment is brought serious pollution to environment.Because Sodium Sulphide content is high and to the toxic action of organic sphere, it is a difficult problem that the biological chemistry of sodium sulphite depilation raffinate purifies.From waste water, removing sulfide now has not been technical problem, but a cost issues.Another problem is to make hide fiber reach sufficient separation with large quantities of lime.Lime and calcium salt have increased mud amount, thereby have increased the transport charge of the first step and the second step mud.A large amount of lime consumptions has also increased liming and has washed the difficulty of protein recovery in the graywall body lotion.
Summary of the invention
Ashless, the alkali sulfide free depilation liming treatment method of a kind of goatskin that the present invention seeks to be directed against the deficiency of prior art and provide.Be characterized in that this method do not use sodium sulphite, Sodium sulfhydrate and lime, reduced the pollution in the preparing leather from goatskin process significantly.
The object of the invention is realized that by following measure the umber of wherein said each raw material is parts by weight except that specified otherwise.
Ashless, the alkali sulfide free depilation liming treatment method of preparing leather from goatskin may further comprise the steps:
(1) immersion
Get 100 parts of rawhides, go into drum, in rotary drum, add 200～300 parts in the water of 25～30 ℃ of temperature, 0.2～0.3 part of peregal; 0.4～0.5 part of soda ash, 0.10～0.15 part in MERPIN 8000 sterilant are visitd 0.3～0.4 part of nurse AN-C grease-removing agent, change 15 minutes; Stopped 15 minutes, totally 4 times, add 0.4～0.5 part of soda ash again, changeed 15 minutes; Stopped 15 minutes, totally 4 times, to change 5 minutes in per then 2 hours, control pH value is 9.2～9.5; Totally 20～24 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water;
(2) pre-treatment
In above-mentioned rotary drum, add 100～150 parts in the water of 25～30 ℃ of temperature, 0.5～0.8 part of pretreating agent changeed 20～30 minutes, stopped 20～30 minutes, and totally 4 times, changeed 3 minutes in per then 2 hours, totally 12～18 hours, control water;
(3) depilation
In above-mentioned rotary drum, add 50～70 parts in 35～40 ℃ of water of temperature, 0.3～0.6 part in ammonium sulfate changeed 60～90 minutes; Regulating the pH value is 8.0～8.5, and the adding vigor is 0.1～0.3 part of the mixing enzyme preparation of 50,000 units/gram, changes 60～90 minutes; The inspection hair has fallen, control water, washing;
(4) expand
In above-mentioned rotary drum, add 80～100 parts in the water of 22～25 ℃ of temperature, 1.0～2.0 parts of caustic dip auxiliary agents rotated 20～30 minutes; Divide three times and add 2～3 parts of swelling agents, add at every turn and rotated 20～30 minutes, stopped 30～60 minutes; Changeed 5 minutes, and totally 16～24 hours, went out drum in per then 2 hours; Fleshing, split is weighed;
(5) dealkalize, softening
80～100 parts in the water that in above-mentioned rotary drum, adds 30～35 ℃ of temperature, 1.0～1.5 parts in ammonium sulfate, 0.2～0.4 part in formic acid; Rotated 40～60 minutes; Regulating the pH value is 8.0～8.5, adds 0.5～0.8 part of ORAPON OO macerating enzyme then, visits 0.4～0.6 part of nurse AN-C grease-removing agent; Rotated washing 90～120 minutes;
(6) pickling
50～100 parts in the water that in above-mentioned rotary drum, adds 20～22 ℃, 5～8 parts of salt changeed 10～15 minutes; Add 0.3～0.5 part in formic acid, changeed 0.5～0.8 part in sulfuric acid 20～30 minutes; Divide 2 times and add, 20～30 minutes at interval, be rotated further 120～150 minutes; Control pH value is 2.2～2.8, gets into chrome tanning then;
Wherein, pretreating agent is a peregal: urea: the mass ratio of sodium hydroxide is 1.0: 1.5: 1.5～2.0: 1.0: 1.0 a mixture;
Mixing enzyme preparation is 2709 proteolytic enzyme: 1398 proteolytic enzyme: the mass ratio of lypase 6: 2: 1～8: 3:: 2 mixture;
The caustic dip auxiliary agent is a diethylamine: Whitfield's ointment: the mass ratio of formaldehyde is 1.0: 0.5: 0.5～2.0: 1.0: 1.0,45 ℃ of temperature of reaction, the condenses that 2 hours reaction times made;
Swelling agent is any in thanomin, diethylolamine or the trolamine.
The pickling goatskin outward appearance that the present invention makes has identical outward appearance and feel for white with the pickled skin that the grey alkaline process of tradition makes, and can directly get into chrome tanning process.
The present invention has following advantage:
1, do not use sodium sulphite, Sodium sulfhydrate and lime, reduce the pollution in the process hides process significantly, the waste water that this technology is discharged more is prone to handle, and large quantities of lime throw out and residue in the traditional technology can not occur.
2, eliminated the maximum operation of this water loss of graywall washing, because of the calcium dirt is few, softening washing time and washing amount reduce when softening, 20%～40% of the nearly total wastewater discharge of economizing on water thus.
3, before using mixed enzyme to handle, skin has been carried out pre-treatment with chemical material, make hair root loosening, enzyme can carry out when handling quickly and safely, thus protection skin grain is injury-free, and the cortex loss is few.
4, technology of the present invention reduces about 20h than the traditional technology production cycle, and water saving, economize on electricity are saved basic material consumption, wastewater treatment materials consumption, mechanical means consumption and reduced by 3～5 yuan/m of comprehensive cost
2(or increasing by 3～5 yuan of profits).
5, overcome the pH value mutation that exists in traditional depilation liming technology and make the graywall non-homogeneous expansion even, the limiting material infiltration is poor, and the liming time such as grows at shortcoming, has reduced the loose side rate, and quality product is more stable.
Specific embodiments
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1: the goat shoe upper leather production technique
(1) immersion
Get the rawhide double centner, go into drum, in rotary drum, add 200 kilograms in the water of 25 ℃ of temperature, 0.2 kilogram of peregal, 0.4 kilogram of soda ash; 0.1 kilogram in MERPIN 8000 sterilant are visitd 0.3 kilogram of nurse AN-C grease-removing agent, change 15 minutes, stop totally 4 times 15 minutes; Add 0.4 kilogram of soda ash again, changeed 15 minutes, stopped 15 minutes, totally 4 times, changeed 5 minutes in per then 2 hours; Control pH value is 9.2, and totally 20 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water.
(2) pre-treatment
The water double centner and the peregal that in above-mentioned rotary drum, add 30 ℃ of temperature: urea: the mass ratio of sodium hydroxide is 1.0: 1.5:: 0.5 kilogram of 1.5 pretreating agent, changeed 20 minutes, stopped 20 minutes; Totally 4 times; Changeed 3 minutes in per then 2 hours, totally 12 hours, control water.
(3) depilation
In above-mentioned rotary drum, adding temperature is 50 kilograms in 35 ℃ of water, and 0.3 kilogram in ammonium sulfate changeed 60 minutes; Regulating the pH value is 8.0; The adding vigor is 2709 proteolytic enzyme of 50,000 units/gram: 1398 proteolytic enzyme: 0.1 kilogram in 6: 2: 1 mixture of the mass ratio of lypase, changeed 60 minutes, and the inspection hair has fallen; Control water, washing.
(4) expand
In above-mentioned rotary drum, add 80 kilograms in the water of 22 ℃ of temperature, diethylamine: Whitfield's ointment: the mass ratio of formaldehyde is 1.0:: 0.5:: 0.5,45 ℃ of temperature of reaction, 1.0 kilograms of the condensess that 2 hours reaction times made; Rotated 30 minutes, and divided three times and add 2 kilograms of thanomins, add at every turn and rotated 20 minutes, stopped 30 minutes; Changeed 5 minutes, and totally 16 hours, went out drum in per then 2 hours; Fleshing, split is weighed.
(5) dealkalize, softening
80 kilograms in the water that in above-mentioned rotary drum, adds 30 ℃ of temperature, 1.0 kilograms in ammonium sulfate, 0.2 kilogram in formic acid rotated 40 minutes, and regulating the pH value is 8.0, adds 0.5 kilogram of ORAPON OO macerating enzyme then, visits 0.4 kilogram of nurse AN-C grease-removing agent, rotates 90 minutes, washes.
(6) pickling
In above-mentioned rotary drum, add 50 kilograms in the water of 20 ℃ of temperature, 5 kilograms of salt changeed 10 minutes, 0.3 kilogram in adding formic acid; Changeed 20 minutes, 0.5 kilogram in sulfuric acid divides 2 addings, 20 minutes at interval; Be rotated further 120 minutes, control pH value is 2.8, parks 10h, gets into chrome tanning then.
Embodiment 2: goat skin gloves leather technology
(1) immersion
Get the rawhide double centner, go into drum, in rotary drum, add 300 kilograms in the water of 30 ℃ of temperature, 0.3 kilogram of peregal, 0.5 kilogram of soda ash; 0.15 kilogram in MERPIN 8000 sterilant are visitd 0.4 kilogram of nurse AN-C grease-removing agent, change 15 minutes, stop totally 4 times 15 minutes; Add 0.5 kilogram of soda ash again, changeed 15 minutes, stopped 15 minutes, totally 4 times, changeed 5 minutes in per then 2 hours; Control pH value is 9.5, and totally 20 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water.
(2) pre-treatment
150 kilograms in the water and the peregal that in above-mentioned rotary drum, add 30 ℃ of temperature: urea: the quality of sodium hydroxide is 2.0: 1.0: 1.0 0.8 kilogram of a pretreating agent, changes 30 minutes, stopped 30 minutes, and totally 4 times, changeed 3 minutes in per then 2 hours, totally 18 hours, control water.
(3) depilation
In above-mentioned rotary drum, add temperature and be 40 ℃ 70 kilograms in water, 0.6 part in ammonium sulfate changeed 60 minutes; Regulating the pH value is 8.5; The adding vigor is 2709 proteolytic enzyme of 50,000 units/gram: 1398 proteolytic enzyme: 0.3 kilogram in 8: 3: 2 mixture of the mass ratio of lypase, changeed 90 minutes, and the inspection hair has fallen; Control water, washing.
(4) expand
In above-mentioned rotary drum, add the water double centner of 25 ℃ of temperature, diethylamine: Whitfield's ointment: the mass ratio of formaldehyde is 2.0:: 1.0:: 1.0,45 ℃ of temperature of reaction, 2.0 kilograms of the condensess that 2 hours reaction times made; Rotated 30 minutes, and divided three times and add 3 kilograms of diethylolamine, add at every turn and rotated 30 minutes, stopped 60 minutes; Changeed 5 minutes, and totally 24 hours, went out drum in per then 2 hours; Fleshing, split is weighed.
(5) dealkalize, softening
The water double centner that in above-mentioned rotary drum, adds 35 ℃ of temperature, 1.5 kilograms in ammonium sulfate, 0.4 kilogram in formic acid rotated 60 minutes, and regulating the pH value is 8.5, adds 0.8 kilogram of ORAPON OO macerating enzyme then, visits 0.6 kilogram of nurse AN-C grease-removing agent, rotates washing 120 minutes.
(6) pickling
In above-mentioned rotary drum, add the water double centner of 22 ℃ of temperature, 8.0 kilograms of salt changeed 15 minutes, added 0.5 kilogram in formic acid; Changeed 30 minutes, 0.8 kilogram in sulfuric acid divides 2 addings, 30 minutes at interval; Be rotated further 150 minutes, control pH value is 2.2, parks 10h, gets into chrome tanning then.
Embodiment 3: goat leather for making garment technology
(1) immersion
Get the rawhide double centner, go into drum, in rotary drum, add 250 kilograms in the water of 28 ℃ of temperature, 0.25 kilogram of peregal, 0.45 kilogram of soda ash; 0.13 kilogram in MERPIN 8000 sterilant are visitd 0.35 kilogram of nurse AN-C grease-removing agent, change 15 minutes, stop totally 4 times 15 minutes; Add 0.45 kilogram of soda ash again, changeed 15 minutes, stopped 15 minutes, totally 4 times, changeed 5 minutes in per then 2 hours; Control pH value is 9.4, and totally 22 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water.
(2) pre-treatment
130 kilograms in the water and the peregal that in above-mentioned rotary drum, add 25 ℃ of temperature: urea: the mass ratio of sodium hydroxide is 1.5: 1.0: 1.5 0.7 kilogram of a pretreating agent, changes 25 minutes, stopped 25 minutes, and totally 4 times, changeed 3 minutes in per then 2 hours, totally 15 hours, control water.
(3) depilation
In above-mentioned rotary drum, add temperature and be 38 ℃ 60 kilograms in water, 0.5 part in ammonium sulfate changeed 80 minutes; Regulating the pH value is 8.3, and the adding vigor is 2709 proteolytic enzyme of 50,000 units/gram: 1398 proteolytic enzyme: 0.2 kilogram in 7: 2: 2 mixture of the mass ratio of lypase, changeed 70 minutes; The inspection hair has fallen; Otherwise be rotated further control water, washing.
(4) expand
In above-mentioned rotary drum, add 90 kilograms in the water of 25 ℃ of temperature, diethylamine: Whitfield's ointment: the mass ratio of formaldehyde is 1.5:: 0.7:: 0.8,45 ℃ of temperature of reaction, 1.5 kilograms of the condensess that 2 hours reaction times made; Rotated 25 minutes, and divided three times and add 2.5 kilograms of trolamines, add at every turn and rotated 25 minutes, stopped 45 minutes; Changeed 5 minutes, and totally 18 hours, went out drum in per then 2 hours; Fleshing, split is weighed.
(5) dealkalize, softening
90 kilograms in the water that in above-mentioned rotary drum, adds 33 ℃ of temperature, 1.25 kilograms in ammonium sulfate, 0.3 kilogram in formic acid rotated 50 minutes, and regulating the pH value is 8.3, adds 0.60 kilogram of ORAPON OO macerating enzyme then, visits 0.5 kilogram of nurse AN-C grease-removing agent, rotates 100 minutes, washes.
(6) pickling
In above-mentioned rotary drum, add 80 kilograms in the water of 21 ℃ of temperature, 7 kilograms of salt changeed 13 minutes, and 0.4 kilogram in formic acid changeed 25 minutes, and 0.6 kilogram in sulfuric acid divides 2 addings, and interval 30 minutes is rotated further 140 minutes, and controlling the pH value is 2.5, gets into chrome tanning then.
Annotate: visiing nurse AN-C grease-removing agent is that Wuxi Lang Sheng (LANXESS) company produces; MERPIN 8000 sterilant are that German Kang Putaisi (CARPUTEX) company produces; ORAPON OO macerating enzyme is that German TRUMPLER company produces.
Claims (1)
1. ashless, the alkali sulfide free depilation liming treatment method of a preparing leather from goatskin, it is characterized in that this method may further comprise the steps: wherein said raw material umber by weight
(1) immersion
Get 100 parts of rawhides, go into drum, in rotary drum, add 200～300 parts in the water of 25～30 ℃ of temperature, 0.2～0.3 part of peregal; 0.4～0.5 part of soda ash, 0.10～0.15 part in MERPIN 8000 sterilant are visitd 0.3～0.4 part of nurse AN-C grease-removing agent, change 15 minutes; Stopped 15 minutes, totally 4 times, add 0.4～0.5 part of soda ash again, changeed 15 minutes; Stopped 15 minutes, totally 4 times, to change 5 minutes in per then 2 hours, control pH value is 9.2～9.5; Totally 20～24 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water;
(2) pre-treatment
In above-mentioned rotary drum, add 100～150 parts in the water of 25～30 ℃ of temperature, 0.5～0.8 part of pretreating agent changeed 20～30 minutes, stopped 20～30 minutes, and totally 4 times, changeed 3 minutes in per then 2 hours, totally 12～18 hours, control water;
(3) depilation
In above-mentioned rotary drum, add 50～70 parts in 35～40 ℃ of water of temperature, 0.3～0.6 part in ammonium sulfate changeed 60～90 minutes; Regulating the pH value is 8.0～8.5, and the adding vigor is 0.1～0.3 part of the mixing enzyme preparation of 50,000 units/gram, changes 60～90 minutes; The inspection hair has fallen, control water, washing;
(4) expand
In above-mentioned rotary drum, add 80～100 parts in the water of 22～25 ℃ of temperature, 1.0～2.0 parts of caustic dip auxiliary agents rotated 20～30 minutes; Divide three times and add 2～3 parts of swelling agents, add at every turn and rotated 20～30 minutes, stopped 30～60 minutes; Changeed 5 minutes, and totally 16～24 hours, went out drum in per then 2 hours; Fleshing, split is weighed;
(5) dealkalize, softening
80～100 parts in the water that in above-mentioned rotary drum, adds 30～35 ℃ of temperature, 1.0～1.5 parts in ammonium sulfate, 0.2～0.4 part in formic acid; Rotated 40～60 minutes; Regulating the pH value is 8.0～8.5, adds 0.5～0.8 part of ORAPON OO macerating enzyme then, visits 0.4～0.6 part of nurse AN-C grease-removing agent; Rotated washing 90～120 minutes;
(6) pickling
50～100 parts in the water that in above-mentioned rotary drum, adds 20～22 ℃, 5～8 parts of salt changeed 10～15 minutes; Add 0.3～0.5 part in formic acid, changeed 0.5～0.8 part in sulfuric acid 20～30 minutes; Divide 2 times and add, 20～30 minutes at interval, be rotated further 120～150 minutes; Control pH value is 2.2～2.8, gets into chrome tanning then;
Wherein, pretreating agent is a peregal: urea: the mass ratio of sodium hydroxide is 1.0: 1.5: 1.5～2.0: 1.0: 1.0 a mixture;
Mixing enzyme preparation is 2709 proteolytic enzyme: 1398 proteolytic enzyme: 6: 2: 1～8: 3: 2 mixture of the mass ratio of lypase;
The caustic dip auxiliary agent is a diethylamine: Whitfield's ointment: the mass ratio of formaldehyde is 1.0: 0.5: 0.5～2.0: 1.0: 1.0,45 ℃ of temperature of reaction, the condenses that 2 hours reaction times made;
Swelling agent is any in thanomin, diethylolamine or the trolamine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810044364A CN101265506B (en) | 2008-05-08 | 2008-05-08 | Ashless and alkali sulfide free depilation liming treatment method for preparing leather from goatskin |
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| CN200810044364A CN101265506B (en) | 2008-05-08 | 2008-05-08 | Ashless and alkali sulfide free depilation liming treatment method for preparing leather from goatskin |
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| CN101265506B true CN101265506B (en) | 2012-09-05 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760569B (en) * | 2008-12-25 | 2013-05-08 | 峰安皮业股份有限公司 | Leather making bio-pretreatment method |
| CN101445843B (en) * | 2008-12-30 | 2012-08-08 | 国家皮革质量监督检验中心（浙江） | Method for carrying out unhairing and liming treatment without dust and akali sulphide during buffalo hide tanning |
| WO2012017264A1 (en) * | 2010-08-05 | 2012-02-09 | West Bengal University Of Technology | Hide processing methods and compositions |
| CN103789462B (en) * | 2012-11-02 | 2015-10-07 | 深圳市绿微康生物工程有限公司 | Process hides prozyme soaks agent |
| CN103060489B (en) * | 2013-01-08 | 2014-10-22 | 四川大学 | Sheep leather acid swelling treatment method |
| CN105671219B (en) * | 2016-03-04 | 2017-11-28 | 海宁上元皮革有限责任公司 | A kind of tanning production technique |
| CN107460259A (en) * | 2017-09-20 | 2017-12-12 | 安徽乐踏鞋业有限公司 | A kind of production method of buffalo hide upper leather |
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