CN101445843B - Method for carrying out unhairing and liming treatment without dust and akali sulphide during buffalo hide tanning - Google Patents
Method for carrying out unhairing and liming treatment without dust and akali sulphide during buffalo hide tanning Download PDFInfo
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- CN101445843B CN101445843B CN2008101639680A CN200810163968A CN101445843B CN 101445843 B CN101445843 B CN 101445843B CN 2008101639680 A CN2008101639680 A CN 2008101639680A CN 200810163968 A CN200810163968 A CN 200810163968A CN 101445843 B CN101445843 B CN 101445843B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000428 dust Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 102000004190 Enzymes Human genes 0.000 claims abstract description 23
- 108090000790 Enzymes Proteins 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000005554 pickling Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 42
- 238000007654 immersion Methods 0.000 claims description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 230000035617 depilation Effects 0.000 claims description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 21
- 235000017550 sodium carbonate Nutrition 0.000 claims description 21
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 238000002203 pretreatment Methods 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000003518 caustics Substances 0.000 claims description 10
- 230000002879 macerating effect Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000008961 swelling Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 6
- 108090000145 Bacillolysin Proteins 0.000 claims description 3
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 3
- 102000035092 Neutral proteases Human genes 0.000 claims description 3
- 108091005507 Neutral proteases Proteins 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229950000244 sulfanilic acid Drugs 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 9
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 9
- 239000004571 lime Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000010985 leather Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- 239000013049 sediment Substances 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention discloses a method for carrying out unhairing and liming treatment without dust and akali sulphide during buffalo hide tanning. The method sequentially comprises steps of pre-soaking, soaking, pretreatment, unhairing, expanding, dealkalizing, softening and pickling. Sodium sulfide, sodium hydrosulfide and lime are not used in the invention so that pollution during the tanning process is greatly reduced, sewage discharged by the process is treated more easily, and a great amount of lime sediment and residual which is produced in a conventional process does not appear. Limed pelt water wash which is a procedure consuming the greatest amount of water is eliminated; as only a small amount of calcium scale is generated during the softening, water wash time and amount of water for washing are reduced during the softening; hereby, the amount of the saved water is approximately 20-40 percent of the total amount of the discharged sewage. Before the use of a biological enzyme for treatment, peltry undergoes pretreatment by means of using a chemical material, therefore, hair roots are loosened, grain surface of the peltry is protected from being damaged, and leather suffers little loss. Compared with the conventional process, the process of the invention reduces the production period by 20 h, saves water, electricity and the chemical material, and reduces the consumption of sewage disposal materials and the number of mechanical apparatuses.
Description
[technical field]
The present invention relates to the process hides field, relate in particular to preceding depilation liming such as a kind of no lime, alkali sulfide free depilation liming treatment method of Corii Bubali process hides, the particularly tanning of Corii Bubali clothing leather, sofa artificial leather, upper leather etc. and handle.
[technical background]
Since the reform and opening-up, 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, suspended solid and sulfide content are very high in the waste liquid, and the waste liquid post precipitation produces a large amount of mud, and difficult treatment is brought serious pollution to environment.Because Sodium Sulphide content is high, strong to the toxic side effect of organic sphere in the sewage, it is a difficult problem that the biological chemistry of sodium sulphite depilation waste liquor purifies.The removal of sulfides from wastewater has not been technical problem at present, but cost issues.Another problem is to make materials with hide glue fibril reach sufficient separation with large quantities of lime.Lime and calcium salt have increased the trucking costs of mud amount and mud, and a large amount of lime consumption of while also causes liming and washes the difficulty of protein recovery in the graywall body lotion.
[summary of the invention]
The object of the invention is exactly the problem that exists in the prior art in order to solve, and proposes a kind of ashless, alkali sulfide free depilation liming treatment method of Corii Bubali process hides, can reduce the pollution in the Corii Bubali process hides process.
For realizing above-mentioned purpose, patent of the present invention has proposed a kind of ashless, alkali sulfide free depilation liming treatment method of Corii Bubali process hides, may further comprise the steps successively: preimpregnation water, immersion, pre-treatment, depilation, expansion, dealkalize, softening, pickling.
As preferably, the operation of each step is following:
Preimpregnation water: get rawhide and go into rotary drum, and in rotary drum, add entry, immersion agent BH-C, soda ash, MERPIN 8000 sterilant, visit nurse AN-C grease-removing agent, changeed 30 minutes, stopped 30 minutes, circulate more than 2 times, go out bulging fleshing then;
Immersion: in rotary drum, add entry, immersion agent BH-C, soda ash, MERPIN 8000 sterilant again, visit nurse AN-C grease-removing agent, changeed 15 minutes, stopped 15 minutes; Circulation adds soda ash more than 2 times then, changes 15 minutes; Stopped 15 minutes, circulation was changeed 5 minutes more than 2 times in per then 2 hours; Control pH value is 9.2-9.5, totally 20～24 hours;
Pre-treatment: in above-mentioned rotary drum, add entry, pretreating agent, changeed 30 minutes, stopped 30 fens, circulation was changeed totally 18～24 hours 3 minutes in per then 2 hours more than 2 times;
Depilation: in above-mentioned rotary drum, add entry, ammonium sulfate, changeed 60～90 minutes, regulating the pH value is 8.0～8.5, adds 0.2～0.3 part of mixing enzyme preparation again, changes 60～90 minutes;
Expand: in above-mentioned rotary drum, add entry, caustic dip auxiliary agent, rotate after 10 minutes, divide three times again and add swelling agent, add at every turn and rotated 30 minutes, stopped 30 minutes, changeed 5 minutes, and totally 18～24 hours, went out drum, fleshing, split then, weigh in per then 2 hours;
Dealkalize: in above-mentioned rotary drum, add entry, ammonium sulfate, formic acid, rotated 60～90 minutes, regulating the pH value is 8.0～8.5;
Softening: as in above-mentioned rotary drum, to add entry, ammonium sulfate, ORAPON OO macerating enzyme, rotated 60～360 minutes, softening complete after washing;
Pickling: in above-mentioned rotary drum, add entry, salt, changeed 10 minutes, add formic acid again, changeed 20 minutes, divide 2 times again and add sulfuric acid, each 30 minutes at interval, add the back and rotated 120～150 minutes, control pH value is 2.2～2.8, gets into chrome tanning then.
As preferably, the processing parameter of each step is following:
Preimpregnation water: get 100 parts of rawhides, go into drum, in rotary drum, add 25～30 ℃ 200～300 parts in water; 0.1～0.2 part of immersion agent BH-C, 0.4～0.5 part of soda ash, 0.10～0.15 part in MERPIN 8000 sterilant; Visit 0.1～0.2 part of nurse AN-C grease-removing agent, changeed 30 minutes, stopped 30 minutes; Totally 4 times, go out bulging fleshing then;
Immersion: in above-mentioned rotary drum, add 25～30 ℃ 200～300 parts in water, 0.2～0.3 part of immersion agent BH-C, 0.4～0.5 part of soda ash, 0.10～0.15 part in MERPIN 8000 sterilant; Visit 0.2～0.4 part of nurse AN-C grease-removing agent, changeed 15 minutes, stopped totally 4 times 15 minutes; Add 0.4～0.5 part of soda ash, changeed 15 minutes, stopped totally 4 times 15 minutes; Changeed 5 minutes in per then 2 hours, control pH value is 9.2 ~ 9.5, totally 20～24 hours;
Pre-treatment: in above-mentioned rotary drum, add 25～30 ℃ 100～150 parts in water, 0.8～1.2 part of pretreating agent changeed 30 minutes, stopped 30 fens, totally 4 times, changeed totally 18～24 hours 3 minutes in per then 2 hours;
Depilation: in above-mentioned rotary drum, add 50～70 parts in 35～40 ℃ of water, 0.6～0.8 part in ammonium sulfate changeed 60 ~ 90 minutes, and adjusting pH value is 8.0～8.5, and the adding vigor is 0.2～0.3 part of the mixing enzyme preparation of 50,000 units/gram, changes 60～90 minutes;
Expand: in above-mentioned rotary drum, add 22～25 ℃ 60～80 parts in water, 1.0～1.5 parts of caustic dip auxiliary agents rotated 10 minutes; Divide three times and add 2.0～3.0 parts of swelling agents, add at every turn and rotated 30 minutes, stopped 30 minutes; Changeed 5 minutes, and totally 18～24 hours, went out drum in per then 2 hours; Fleshing, split is weighed;
Dealkalize: in above-mentioned rotary drum, add 30～35 ℃ 60～80 parts in water, 1.0～1.5 parts in ammonium sulfate, 0.2～0.4 part in formic acid rotated 60～90 minutes, and regulating the pH value is 8.0～8.5;
Softening: in above-mentioned rotary drum, add 30～35 ℃ 80～100 parts in water, 0.2～0.3 part in ammonium sulfate, 0.8～1.2 part of ORAPON OO macerating enzyme rotated 60～360 minutes, softened complete after washing;
Pickling: in above-mentioned rotary drum, add 20～22 ℃ 50～80 parts in water, 6～8 parts of salt changeed 10 minutes; Add 0.3～0.5 part in formic acid, changeed 0.5～0.8 part in sulfuric acid 20 minutes; Divide 2 times and add, 30 minutes at interval, add the back and rotated 120～150 minutes; Control pH value is 2.2～2.8, gets into chrome tanning then.
As preferably, the pretreating agent that adds in the said pre-treatment step is the tensio-active agent peregal: urea: the mass ratio of sodium hydroxide is 0.5～1.0: 1～2: 1～2 mixture.
As preferably, the mixing enzyme preparation that adds in the said epilation step is a Sumizyme MP: neutral protease: the mass ratio of lypase is 8: 3: 2 a mixture.
As preferably, the caustic dip auxiliary agent that adds in the said expansion step is a diethylamine: Whitfield's ointment: the mass ratio of sodium hydroxide is 1～2.0: 0.5～1.0: 1.0～2.5, and 45 ℃ of temperature of reaction, the condenses that 2 hours reaction times made.
As preferably, the swelling agent that adds in the said expansion step is a thanomin: sulfanilic acid: the mass ratio of sodium hydroxide is 0.5～1.0: 0.5～1.5: 0.5～1.5 mixture.
The beneficial effect of patent of the present invention: the present invention does not use sodium sulphite, Sodium sulfhydrate and lime; Realized ashless, alkali sulfide free depilation; Reduced 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.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, and conserve water is near 20%～40% of total wastewater discharge thus.Before using enzyme to handle, with chemical material rawhide has been carried out pre-treatment, made hair root loosening, enzyme can carry out when handling quickly and safely, thereby protection rawhide grain is injury-free, and the cortex loss is few.Technology of the present invention reduces about 20h than the traditional technology production cycle, and water saving, economize on electricity are saved chemical materials consumption, reduce the wastewater treatment materials consumption, reduced mechanical means consumption, reduce comprehensive cost 3-5 unit/m.Shortcomings such as overcome the pH value mutation that exists in traditional depilation liming technology and made liming skin non-homogeneous expansion even, the limiting material infiltration is poor, and the liming time is long have reduced the loose side rate, and quality product is more stable.
[embodiment]
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: Corii Bubali upper leather production technique
(1) preimpregnation water
Get the rawhide double centner, go into drum, in rotary drum, add 25 ℃ 200 kilograms in water, 0.1 kilogram of immersion agent BH-C; 0.4 kilogram of soda ash, 0.10 kilogram in MERPIN 8000 sterilant are visitd 0.1 kilogram of nurse AN-C grease-removing agent, change 30 minutes; Stopped 30 minutes, and totally 4 times, went out bulging fleshing then.
(2) immersion
200 kilograms in the water that in above-mentioned rotary drum, adds 25 ℃, 0.2 kilogram of immersion agent BH-C, 0.4 kilogram of soda ash, 0.10 kilogram in MERPIN 8000 sterilant are visitd 0.2 kilogram of nurse AN-C grease-removing agent; Changeed 15 minutes, stopped 15 minutes, totally 4 times, add 0.4 kilogram of soda ash, changeed 15 minutes; Stopped 15 minutes, totally 4 times, to change 5 minutes in per then 2 hours, control pH value is 9.2; Totally 20 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water.
(3) pre-treatment
The water double centner that in above-mentioned rotary drum, adds 25 ℃, 0.8 kilogram of pretreating agent changeed 30 minutes, stopped 30 fens, totally 4 times, changeed 3 minutes in per then 2 hours, totally 18 hours, control water.
(4) depilation
In above-mentioned rotary drum, add 50 kilograms in 35 ℃ of water, 0.6 kilogram in ammonium sulfate changeed 60 minutes, and regulating pH value is 8.0, and the adding vigor is 0.2 kilogram of the mixing enzyme preparation of 50,000 units/gram, changeed 90 minutes, and inspection mao has been fallen, and controls water, washes.
(5) expand
60 kilograms in the water that in above-mentioned rotary drum, adds 22 ℃, 1.0 kilograms of caustic dip auxiliary agents rotated 10 minutes, divided three times and added 2.0 kilograms of swelling agents, added rotation 30 minutes at every turn, stopped 30 minutes, commentaries on classics in per then 2 hours 5 minutes, totally 18 hours, go out drum, fleshing, split is weighed.
(6) dealkalize
60 kilograms in the water that in above-mentioned rotary drum, adds 30～35 ℃, 1.0 kilograms in ammonium sulfate, 0.2 kilogram in formic acid rotated 40～60 minutes, and regulating the pH value is 8.0.
(7) softening
80 kilograms in the water that in above-mentioned rotary drum, adds 30～35 ℃, 0.2 kilogram in ammonium sulfate, 0.8 kilogram of ORAPON OO macerating enzyme rotated 60 minutes, softening complete after washing.
(8) pickling
50 kilograms in the water that in above-mentioned rotary drum, adds 20 ℃, 6 kilograms of salt changeed 10 minutes, added 0.3 kilogram in formic acid, changeed 20 minutes, and 0.5 kilogram in sulfuric acid divides 2 adding, interval 30 minutes, rotation is 120 minutes after adding, and controlling the pH value is 2.8, gets into chrome tanning then.
Embodiment 2: Corii Bubali clothing leather technology
(1) preimpregnation water
Get the rawhide double centner, go into drum, in rotary drum, add 28 ℃ 250 kilograms in water, 0.15 kilogram of immersion agent BH-C; 0.45 kilogram of soda ash, 0.13 kilogram in MERPIN 8000 sterilant are visitd 0.15 kilogram of nurse AN-C grease-removing agent, change 30 minutes; Stopped 30 minutes, and totally 4 times, went out bulging fleshing then.
(2) immersion
250 kilograms in the water that in above-mentioned rotary drum, adds 28 ℃, 0.25 kilogram of immersion agent BH-C, 0.45 kilogram of soda ash, 0.13 kilogram in MERPIN 8000 sterilant are visitd 0.3 kilogram of nurse AN-C grease-removing agent; Changeed 15 minutes, stopped 15 minutes, totally 4 times, add 0.45 kilogram of soda ash, changeed 15 minutes; Stopped 15 minutes, totally 4 times, to change 5 minutes in per then 2 hours, control pH value is 9.3; Totally 22 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water.
(3) pre-treatment
120 kilograms in the water that in above-mentioned rotary drum, adds 28 ℃, 1.0 kilograms of pretreating agents changeed 30 minutes, stopped 30 fens, totally 4 times, changeed 3 minutes in per then 2 hours, totally 20 hours, control water.
(4) depilation
In above-mentioned rotary drum, add 60 kilograms in 38 ℃ of water, 0.7 kilogram in ammonium sulfate changeed 80 minutes, and regulating pH value is 8.3, and the adding vigor is 0.25 kilogram of the mixing enzyme preparation of 50,000 units/gram, changeed 70 minutes, and inspection mao has been fallen, and controls water, washes.
(5) expand
70 kilograms in the water that in above-mentioned rotary drum, adds 24 ℃, 1.3 kilograms of caustic dip auxiliary agents rotated 10 minutes, divided three times and added 2.5 kilograms of swelling agents, added rotation 30 minutes at every turn, stopped 30 minutes, commentaries on classics in per then 2 hours 5 minutes, totally 21 hours, go out drum, fleshing, split is weighed.
(6) dealkalize
70 kilograms in the water that in above-mentioned rotary drum, adds 30～35 ℃, 1.2 kilograms in ammonium sulfate, 0.3 kilogram in formic acid rotated 70 minutes, and regulating the pH value is 8.2.
(7) softening
90 kilograms in the water that in above-mentioned rotary drum, adds 32 ℃, 0.25 kilogram in ammonium sulfate, 1.0 kilograms of ORAPON OO macerating enzymes rotated 240 minutes, softened complete after washing.
(8) pickling
70 kilograms in the water that in above-mentioned rotary drum, adds 21 ℃, 7 kilograms of salt changeed 10 minutes, added 0.4 kilogram in formic acid, changeed 20 minutes, and 0.7 kilogram in sulfuric acid divides 2 adding, interval 30 minutes, rotation is 140 minutes after adding, and controlling the pH value is 2.4, gets into chrome tanning then.
Embodiment 3: Corii Bubali sofa artificial leather technology
(1) preimpregnation water
Get the rawhide double centner, go into drum, in rotary drum, add 30 ℃ 300 kilograms in water, 0.2 kilogram of immersion agent BH-C; 0.5 kilogram of soda ash, 0.15 kilogram in MERPIN 8000 sterilant are visitd 0.2 kilogram of nurse AN-C grease-removing agent, change 30 minutes; Stopped 30 minutes, and totally 4 times, went out bulging fleshing then.
(2) immersion
300 kilograms in the water that in above-mentioned rotary drum, adds 30 ℃, 0.3 kilogram of immersion agent BH-C, 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; Changeed 15 minutes, stopped 15 minutes, totally 4 times, add 0.5 kilogram of soda ash, changeed 15 minutes; Stopped 15 minutes, totally 4 times, to change 5 minutes in per then 2 hours, control pH value is 9.5; Totally 24 hours, inspection immersion skin body bone was soft, and otch all passes through the heart, control water.
(3) pre-treatment
150 kilograms in the water that in above-mentioned rotary drum, adds 30 ℃, 1.2 kilograms of pretreating agents changeed 30 minutes, stopped 30 fens, totally 4 times, changeed 3 minutes in per then 2 hours, totally 24 hours, control water.
(4) depilation
In above-mentioned rotary drum, add 70 kilograms in 40 ℃ of water, 0.8 kilogram in ammonium sulfate changeed 90 minutes, and regulating pH value is 8.5, and the adding vigor is 0.3 kilogram of the mixing enzyme preparation of 50,000 units/gram, changeed 60 minutes, and inspection mao has been fallen, and controls water, washes.
(5) expand
80 kilograms in the water that in above-mentioned rotary drum, adds 25 ℃, 1.5 kilograms of caustic dip auxiliary agents rotated 10 minutes, divided three times and added 3.0 kilograms of swelling agents, added at every turn and rotated 30 minutes, stopped 30 minutes, and commentaries on classics in per then 2 hours 5 minutes is total to
24 hours, go out drum, fleshing, split is weighed.
(6) dealkalize
80 kilograms in the water that in above-mentioned rotary drum, adds 35 ℃, 1.5 kilograms in ammonium sulfate, 0.4 kilogram in formic acid rotated 90 minutes, and adjusting pH value is 8.5.
(7) softening
The water double centner that in above-mentioned rotary drum, adds 35 ℃, 0.3 kilogram in ammonium sulfate, 1.2 kilograms of ORAPON OO macerating enzymes rotated 360 minutes, softening complete after washing.
(8) pickling
80 kilograms in the water that in above-mentioned rotary drum, adds 22 ℃, 8 kilograms of salt changeed 10 minutes, added 0.5 kilogram in formic acid, changeed 20 minutes, and 0.8 kilogram in sulfuric acid divides 2 adding, interval 30 minutes, rotation is 150 minutes after adding, and controlling the pH value is 2.2, gets into chrome tanning then.
Note: immersion agent BH-C, 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.
The foregoing description is to explanation of the present invention, is not to qualification of the present invention, any scheme after the simple transformation of the present invention is all belonged to protection scope of the present invention.
Claims (2)
1. ashless, the alkali sulfide free depilation liming treatment method of a Corii Bubali process hides is characterized in that: may further comprise the steps successively: preimpregnation water, immersion, pre-treatment, depilation, expansion, dealkalize, softening, pickling, and the operation of each step is following:
Preimpregnation water: get rawhide and go into rotary drum, and in rotary drum, add entry, immersion agent BH-C, soda ash, MERPIN8000 sterilant, visit nurse AN-C grease-removing agent, changeed 30 minutes, stopped 30 minutes, circulate more than 2 times, go out bulging fleshing then;
Immersion: in rotary drum, add entry, immersion agent BH-C, soda ash, MERPIN 8000 sterilant again, visit nurse AN-C grease-removing agent, changeed 15 minutes, stopped 15 minutes; Circulation adds soda ash more than 2 times then, changes 15 minutes; Stopped 15 minutes, circulation was changeed 5 minutes more than 2 times in per then 2 hours; Control pH value is 9.2-9.5, totally 20～24 hours;
Pre-treatment: in above-mentioned rotary drum, add entry, pretreating agent, changeed 30 minutes, stopped 30 fens, circulation was changeed totally 18～24 hours 3 minutes in per then 2 hours more than 2 times;
Depilation: in above-mentioned rotary drum, add entry, ammonium sulfate, changeed 60～90 minutes, regulating the pH value is 8.0～8.5, adds 0.2～0.3 part of mixing enzyme preparation again, changes 60～90 minutes;
Expand: in above-mentioned rotary drum, add entry, caustic dip auxiliary agent, rotate after 10 minutes, divide three times again and add swelling agent, add at every turn and rotated 30 minutes, stopped 30 minutes, changeed 5 minutes, and totally 18～24 hours, went out drum, fleshing, split then, weigh in per then 2 hours;
Dealkalize: in above-mentioned rotary drum, add entry, ammonium sulfate, formic acid, rotated 60～90 minutes, regulating the pH value is 8.0～8.5;
Softening: as in above-mentioned rotary drum, to add entry, ammonium sulfate, ORAPON OO macerating enzyme, rotated 60～360 minutes, softening complete after washing;
Pickling: in above-mentioned rotary drum, add entry, salt, changeed 10 minutes, add formic acid again; Changeed 20 minutes, and divided 2 times again and add sulfuric acid, each 30 minutes at interval; Add the back and rotated 120～150 minutes, control pH value is 2.2～2.8, gets into chrome tanning then; The agent BH-C that wherein soaks, 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; The pretreating agent that adds in the said pre-treatment step is the tensio-active agent peregal: urea: the mass ratio of sodium hydroxide is 0.5～1.0: 1～2: 1～2 mixture; The mixing enzyme preparation that adds in the said epilation step is a Sumizyme MP: neutral protease: the mass ratio of lypase is 8: 3: 2 a mixture; The caustic dip auxiliary agent that adds in the said expansion step is a diethylamine: Whitfield's ointment: the mass ratio of sodium hydroxide is 1～2.0: 0.5～1.0: 1.0～2.5; 45 ℃ of temperature of reaction; The condenses that 2 hours reaction times made, the swelling agent that adds in the said expansion step are thanomin: sulfanilic acid: the mass ratio of sodium hydroxide is 0.5～1.0: 0.5～1.5: 0.5～1.5 mixture.
2. ashless, the alkali sulfide free depilation liming treatment method of a Corii Bubali process hides is characterized in that: may further comprise the steps successively: preimpregnation water, immersion, pre-treatment, depilation, expansion, dealkalize, softening, pickling, and the processing parameter of each step is following:
Preimpregnation water: get 100 parts of rawhides, go into drum, in rotary drum, add 25～30 ℃ 200～300 parts in water; 0.1～0.2 part of immersion agent BH-C, 0.4～0.5 part of soda ash, 0.10～0.15 part in MERPIN 8000 sterilant; Visit 0.1～0.2 part of nurse AN-C grease-removing agent, changeed 30 minutes, stopped 30 minutes; Totally 4 times, go out bulging fleshing then;
Immersion: in above-mentioned rotary drum, add 25～30 ℃ 200～300 parts in water, 0.2～0.3 part of immersion agent BH-C, 0.4～0.5 part of soda ash, 0.10～0.15 part in MERPIN 8000 sterilant; Visit 0.2～0.4 part of nurse AN-C grease-removing agent, changeed 15 minutes, stopped totally 4 times 15 minutes; Add 0.4～0.5 part of soda ash, changeed 15 minutes, stopped totally 4 times 15 minutes; Changeed 5 minutes in per then 2 hours, control pH value is 9.2～9.5, totally 20～24 hours;
Pre-treatment: in above-mentioned rotary drum, add 25～30 ℃ 100～150 parts in water, 0.8～1.2 part of pretreating agent changeed 30 minutes, stopped 30 fens, totally 4 times, changeed totally 18～24 hours 3 minutes in per then 2 hours;
Depilation: in above-mentioned rotary drum, add 50～70 parts in 35～40 ℃ of water, 0.6～0.8 part in ammonium sulfate changeed 60～90 minutes, and adjusting pH value is 8.0～8.5, and the adding vigor is 0.2～0.3 part of the mixing enzyme preparation of 50,000 units/gram, changes 60～90 minutes;
Expand: in above-mentioned rotary drum, add 22～25 ℃ 60～80 parts in water, 1.0～1.5 parts of caustic dip auxiliary agents rotated 10 minutes; Divide three times and add 2.0～3.0 parts of swelling agents, add at every turn and rotated 30 minutes, stopped 30 minutes; Changeed 5 minutes, and totally 18～24 hours, went out drum in per then 2 hours; Fleshing, split is weighed;
Dealkalize: in above-mentioned rotary drum, add 30～35 ℃ 60～80 parts in water, 1.0～1.5 parts in ammonium sulfate, 0.2～0.4 part in formic acid rotated 60～90 minutes, and regulating the pH value is 8.0～8.5;
Softening: in above-mentioned rotary drum, add 30～35 ℃ 80～100 parts in water, 0.2～0.3 part in ammonium sulfate, 0.8～1.2 part of ORAPON OO macerating enzyme rotated 60～360 minutes, softened complete after washing;
Pickling: in above-mentioned rotary drum, add 20～22 ℃ 50～80 parts in water, 6～8 parts of salt changeed 10 minutes, added 0.3～0.5 part in formic acid; Changeed 20 minutes, 0.5～0.8 part in sulfuric acid divides 2 addings; 30 minutes at interval, add the back and rotated 120～150 minutes, control pH value is 2.2～2.8; Get into chrome tanning then, the agent BH-C that wherein soaks, 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; The pretreating agent that adds in the said pre-treatment step is the tensio-active agent peregal: urea: the mass ratio of sodium hydroxide is 0.5～1.0: 1～2: 1～2 mixture; The mixing enzyme preparation that adds in the said epilation step is a Sumizyme MP: neutral protease: the mass ratio of lypase is 8: 3: 2 a mixture; The caustic dip auxiliary agent that adds in the said expansion step is a diethylamine: Whitfield's ointment: the mass ratio of sodium hydroxide is 1～2.0: 0.5～1.0: 1.0～2.5; 45 ℃ of temperature of reaction; The condenses that 2 hours reaction times made, the swelling agent that adds in the said expansion step are thanomin: sulfanilic acid: the mass ratio of sodium hydroxide is 0.5～1.0: 0.5～1.5: 0.5～1.5 mixture.
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| CN101798605B (en) * | 2010-03-16 | 2012-10-31 | 浙江通天星集团股份有限公司 | Energy saving and emission reduction method for retanning and dyeing high-strength split from cattle hide for furniture |
| EP2601316A4 (en) * | 2010-08-05 | 2017-07-05 | West Bengal University Of Technology | Hide processing methods and compositions |
| TW201309864A (en) * | 2011-08-22 | 2013-03-01 | Jollity Entpr Co Ltd | Depilation method of animal skin |
| CN102952907B (en) * | 2011-08-26 | 2015-05-13 | 约泰实业股份有限公司 | Method for depilating animal skin |
| CN102505057B (en) * | 2011-10-21 | 2013-10-16 | 中国皮革和制鞋工业研究院 | Cyclic utilization method of chrome tanning waste liquid |
| CN102505056B (en) * | 2011-10-21 | 2013-10-16 | 中国皮革和制鞋工业研究院 | Hair-protection unhairing and liming waste liquor recycling method |
| CN102517407B (en) * | 2011-11-28 | 2013-07-24 | 郑州科信化工有限公司 | Processing method of leather semi-finished product |
| CN104711379B (en) * | 2015-02-12 | 2017-05-03 | 四川大学 | Enzyme unhairing method for removing damage to cowhide leather grain surface |
| 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 |
| CN108220499A (en) * | 2018-02-06 | 2018-06-29 | 海宁文硕科技咨询有限公司 | A kind of leather processing |
| CN110129489B (en) * | 2019-05-23 | 2021-10-01 | 漳州香洲皮革有限公司 | Method for preparing chrome-free pickled skin |
| CN110628857B (en) * | 2019-10-29 | 2021-07-02 | 南宁学院 | Method for extracting collagen from cow leather |
| CN113832263B (en) * | 2021-11-02 | 2022-04-08 | 宁夏金海皮业有限责任公司 | Production method of buffalo hide instead of buffalo hide |
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