CN1302909A - Process for tanning skin of highland schizothoracin and grass carp - Google Patents

Abstract

A process for tanning the skin of highland schizothor acin or grass carp includes such steps as pretreating, defatting, removing scales, coating ash, removing ash, softening, pickling; pre-tanning with rotary drum, chrome tanning, extracting alkali in marking trough, neutralizing, re-tanning with rotary drum, dyeing, drying and finishing. Its advantages include no need of strong toxic material, recovery of waste liquid, high efficiency, short period, low cost and beautiful appearance of tanned skin.

Description

The process for tanning of highland schizothoracin, grass carp fish-skin

The present invention relates to a kind of chemical treatment of fish-skin, the process for tanning of particularly a kind of highland schizothoracin, grass carp fish-skin.

Tibet is located in the plateau, and the fishery aboundresources has advantageous supremacy clause, and the lake group in Tibet is that height above sea level is the highest in the world, scope is maximum, the plateau lake district that quantity is maximum.Wherein surpass 1km2 just have 1003.According to measuring and calculating lake, Tibet, storage fish amount is 136869.705T, and the storage fish amount of rivers is 4060.95T.The kind of fish mainly contains highland schizothoracin, grass carp, also has a kind of comparatively special alepidote-plateau naked carp fish.Chinese patent CN86107461, " method for preparing fish-skin " by name, the method that the document is announced is Brazil thorn perch that is used for tanning Seranidae family, but institute's applicable scope is a kind of special fish, applicable surface is little, used industrial chemicals source difficulty, cost height, be not suitable for outlying inaccessible area and use, bring certain difficulty for the enforcement cause.Chinese patent CN961052740 is called " purposes of the process for tanning of plateau naked carp skin and made fish-skin thereof ".Though can make the special fingerling in Tibet obtain utilizing, can be made into cold-resistant, water-fast, and the comparatively firm leather of quality.But special because of the used fingerling of this technology, only limit to alepidote and this fish and have only the Yang Hu in Tibet just to produce, fish is named as sheep lake naked carp fish, and adaptive surface is narrow.And in the Qinghai-Tibet Platean, highland schizothoracin and grass carp are main fish, belong to medium-sized fish individuality, and only the schizothoracin kind just has tens kinds, Zang Bei particularly, and this type of scale fiss resource is abundant especially, and fails to obtain development and use.Above-mentioned patented technology is not suitable for the fish-skin that this kind of tanning has the squama fish, and its prepared fish skin collagen fiber falls layer easily, and soft-quality is relatively poor; The not enough science of the technology that this patent adopted simultaneously, the raw materials used kind of the operation that has is many, and is wayward, and the used operating time is longer, when tanning, needs use chromium alum, hypertoxic raw material such as saltcake to have and pollutes greatly the problem that waste liquid can not be recycled.This technology also needs the special equipment roller press to throw time increase

The objective of the invention is to realize the process for tanning of highland schizothoracin, grass carp fish-skin, the used industrial chemicals of this method is easy to get, and the operating time is few, the efficient height, simple to operate, cost is low, use in outlying so inaccessible area, suitable Tibet, makes the main fish of Qinghai-Tibet Platean obtain development and use.Cold-resistant water-fast except that having with the prepared fish-skin of this method, scrubbing resistance, good permeability outside resistance to tension is strong, also can have layer, and cutification has advantages such as natural vein.This technology is not used hypertoxic raw material without specific installation, and the recycling of waste liquid energy can reduce pollution.

The tanning of schizothoracin of the present invention, grass carp fish-skin is made of following step: (1) gives treatment process: purpose is sterilization, decontamination, fleshing; (2) degreasing: purpose is with leather surface and inner grease emulsifying and soluble in water fat abstraction; (3) alkali swells, scales: purpose is soluble proteins, Keratin sulfate and the cystine linkage of dissolving intracutaneous, allows the squama of epidermal area separate with corium with reticular layer, the increase of having a rest of the sky between collegen filament; (4) multiple ash: purpose is the soluble proteins that further dissolves intracutaneous; (5) deliming: purpose is that alkali is swollen, and the pelt behind the multiple ash manipulation is immersed in the lime that permeates when removing liming in the acidic solution at intracutaneous, alkaline matter, and the swelling state of elimination pelt makes the soft face of the leather of making careful; (6) softening: purpose is further disperseed collegen filament, the rawhide softness, and extension property is strong behind the finished leather, and is plentiful behind the finished leather, and good hand touch is pickling, and chrome tanning lays the first stone; (7) pickling: the pH-value of regulating pelt is that chrome tanning creates conditions, and hide fiber is further separated, and is beneficial to tanning, and increases the softness of leather body and the trickle degree of fullness and leather body; (8) give and tanning: the natural vein of purpose protection leather surface and lower convergency; (9) chrome tanning: purpose allows pelt become to tan the important procedure of skin, improve the tan shrinkage temperature (TS) of skin and the structural stability of skin protein: (10) propose alkali, neutralization: purpose is to remove free acid unnecessary in the leather, further reinforcing chrome tanning thing combines with collagen protein, and being stuffing, dyeing provides the pH-value condition; (11) retanning: allow the structure of leather be reinforced, and change the leather surface charge and improve washable, sweat proof, alkali resistance, for stuffing dyeing is prepared; (12) stuffing, dyeing: wet leather absorbs oil plant after making tanning, dyestuff, and more soft and full behind the finished leather, moisture-sensitive is tough and tensile not durable.(13 back reason reasons comprise drying, polishing, clean arrangement.

Below each making step is elaborated

(1) the described treating processes of giving, be in rotary drum, pack into fresh fish skin and normal temperature softening water, the weight ratio of fresh fish skin and water is 1: 1, the weight of pressing water adds the salt (CNCL) of 4.5-5.5%, start rotary drum 1 hour, fish-skin is taken out rotary drum, remove the remaining flesh of fish of fish-skin, renew bright salt solution and cleaned in rotary drum 1 hour, salt solution is joined method with aforementioned;

(2) skimming processes, water and wet fish-skin weight are 1: 1 (following each step severe edema due to hypofunction of the spleen weight ratio is identical do not state in addition) in the dosing, by weight adding in water.The OP tensio-active agent octyl phenol of 0.4-0.6%JFC permeate agent and 2-4%, normal temperature rotated 2-3 hour in rotary drum, took out with normal-temperature water then and cleaned half an hour;

(3) the swollen process of scaling of alkali adds normal-temperature water in rotary drum, adds 3-5% in the water, white lime Ca (OH) ₂, add the 0.15-0.3%JFC permeate agent again, more than be weight ratio.The pH value of dosing is 12-14; Rotated 3-5 hour, leather is swollen thick, and transparent feel is arranged, and takes out rotary drum, removes the squama and the reticular layer of fish-skin epidermal area, and the fish-skin clear water of scaling and finishing cleans half an hour; Used dosing is recyclable to be used 1 time again;

(4) multiple grey process is injected water in the paddle-tumble, adds talcum powder (3mgo4SiO by weight ₂H ₂O) 4%, JFC permeate agent 0.15-0.3%, pH value 12-14 drops into wet pelt, soak at room temperature 9-11 hour, per hour stir once with rod, take out pelt and cleaned 10-20 minute with clear water;

(5) deliming process is injected water in the paddle-tumble, adds 1.5-2.5% boric acid by weight, and the 0.15-0.3JFC permeate agent is put into pelt and stirred immersion 1.5-2.5 hour, cleans 10-20 minute with clear water then;

(6) softening process, with paddle-tumble water is heated to 40 ℃-45 ℃, add 0.15-0.25% industry pancreatin by weight, 1.5-3% ammonium chloride, 0.15-0.3%JFC permeate agent, the wet pelt that is preheated to 41 ℃-45 ℃ dropped in the above-mentioned dosing stirred 5-10 minute, finish softening.Its determination methods is for finger extruding pelt, if can stay fingerprint and be and soften successfully.Finish the remollescent pelt and immerse alum [KAL (SO) 12H that contains weight 1% ₂O] stop in the aqueous solution softening;

(7) pickling process, water is injected paddle-tumble, water temperature 20-22 ℃, add 6-8% salt, 0.4-0.6% formic acid (HCHO) by weight, the 0.15-0.3%JFC permeate agent is surveyed PH=1, wet pelt is dropped in this dosing, stirred 1-1.5 hour, and soaked and finished pickling in 12-13 hour, hygrometric skin pH value is 2.5;

(8) pretan process adds entry in rotary drum, press the 1-2% weight ratio and add cationic fat liquor, and the fish-skin of packing into rotates and got final product in 25-35 minute;

(9) chrome tanning process, adding water goes in the rotary drum, add the 15-18% basic chrome sulfate by weight, the 0.15-0.3%JFC permeate agent, 0.8-1.5% peregal 0 transfers pH value between 3.2-4.6 with sodium-acetate or Sulfothiorine, the pelt of packing into, rotated at normal temperatures after 2 hours the quiet 1.5-2.5 of soaking hour, rotated again 1 hour, take out the skin of tanning and take and measure after horse crosses liquid;

(10) carry alkali, N-process, add water and in paddle-tumble, add 0.8-1.5% yellow soda ash by weight, the 0.15-0.3%JFC permeate agent, surveying pH value is 6 ± 1, and chromed tanned leather is packed in the paddle-tumble, soaks at normal temperatures 9-11 hour, intermittently stirs;

(11) retanning process is packed 40-45 ℃ of warm water in the rotary drum into, allocates glutaraldehyde [OHC. (CH into ₂) ₃CHO] 0.4-0.6%, softener sg 0.8-1.2%, with give heat in 40-45 ℃ and raw hide pack in the rotary drum, rotated 3.5-4.5 hour, quiet soaking 3 hours rotated to take out in 1 hour again and thrown water (not dripping even the leather through processing has obviously);

(12) stuffing dyeing course, to be preheated to 58-62 ℃ through the retanning raw hide earlier, 55-65 ℃, the warm water rotary drum of packing into is allocated 8-12% moccasin fatting agent (Sichuan Shi Fangshi leather retanning agent factory product), 0.8-1.2% dyestuff into, the 0.15-0.3%JFC permeate agent in warm water, 0.8-1.2 peregal 0, the skin of tanning of packing into rotates and adds 0.3-0.6% formic acid and 0.8-1.2% laking agent after 25-40 minute, rotates after 25-40 minute again and throws water;

(13) aftertreatment: drying, polishing, clean, arrangement, adopt existing known method, no longer carefully state.

Can be after above-mentioned each course of processing with fresh fish leather finished product raw hide.

The method of tanning fish-skin of the present invention, used industrial chemicals are curriery and chemical industry raw material commonly used, and raw material is easy to get, and consumption is few, not only pollute little, and with low cost.Simple to operate, do not have numerous change blending process, most of technologies only have 1-3 kind industrial chemicals, 2 procedures are with 4 kinds of raw materials, and (12) stuffing dyeing lumps together stuffing and dyeing, only in rotary drum, operate, only use about 1 hour, both can finish complicated degreasing, mordant dyeing, fade, contaminate again, various operation such as washing, stuffing, though this operation is successively with 6 kinds of raw materials, but merge a plurality of operations, time saving and energy saving, improved tanning efficient.In addition in this process for tanning (3), (4), (10) operation be mainly to pollute operation, but used waste liquid all can recycle, and reduced pollution.Because present method has These characteristics, be that use in so outlying inaccessible area, suitable Tibet, can make the main fish resource of Tibet untapped utilization still obtain development and use, help the Economic development of minority area, Tibet.Remove with the prepared fish-skin of present method and to have cold-resistant, water-fast, scrubbing resistance, good permeability outside the strong characteristics of stretching resistance, also can have layer, and cutification has natural vein, and is beautiful, and technical indicator is better than seeing the made leather of Reptilia.This technology need not specific installation, only gets final product with rotary drum or the such common equipment of paddle-tumble basically, can save investment, does not use hypertoxic raw material in the tanning, so the recycling of waste liquid energy can reduce pollution.Every tanning 120 kg fish-skin is 106 hours with naked carp skin technology, only uses 45.05 hours with this technology, and working efficiency improves greatly.

Embodiment:

Select for use the fresh fish skin of the highland schizothoracin of 120kg to carry out tanning.

1, carry out the processing of giving of fresh hide, with the aqueous solution of 120kg clear water preparation salt (NaCL), wherein salts contg is 120kg * 5%=6kg, and salts solution is poured in the rotary drum.Again the highland schizothoracin fresh hide of 120kg is all packed in the rotary drum, start rotary drum at normal temperatures, select 12 revolutions that change for use, rotate after 1 hour fresh hide is taken out, the meat blunt scraper under residual on the leather is scraped off.By with quadrat method complex salt solution, measure after the raw material skin was extracted most of water after input scraping fresh fish skin cleaned and gets after 1 hour then.Obtain 110kg humidogene fish-skin.

2, carry out degreasing, with 110kg clear water preparation octyl phenol solution, content is 110kg * 3%=3.3kg, adds JFC permeate agent 110kg * 0.5%=0.55kg again, selects 12 commentaries on classics, revolution at normal temperatures for use, rotates 2.5 hours.The liquid of skimming cleans half an hour, and water squeezing (do not have and obviously drip) back metering obtains degrease pelt 105kg.

3, alkali swells, goes fish scale and reticular layer to handle.The 105kg clear water packed into prepare Ca (OH) behind the rotary drum ₂Solution, wherein content is 105kg * 4%=42kg, adds JFC permeate agent 105kg * 0.2%=0.21kg again, after solution prepares pelt packed in the rotary drum, select the 12 revolution work of changeing 4 hours, check leather response situation and pH value, this moment, leather was significantly swollen thick, transparent, and pH value is more than 12.This moment leather is taken out epidermis fish scale and the reticular layer that scrapes off more than the skin corium.Method is to scrape off to head from afterbody being placed on leather smooth on the chopping board with blunt scraper.Till the scraping.All leathers were finished 4 hours, and (deciding according to workman or mechanical speed), this skin are handled clean back clear water and cleaned and threw the water metering in 30 minutes and obtain leather 60kg.

4, multiple ash is handled: the 60kg clear water is packed in the paddle-tumble, join (3mgo4sio ₂H ₂O) solution.Its content is 60kg * 4%=2.4kg, and JFC permeate agent 60kg * 0.2%=0.12kg, solution prepare the back leather is dropped in the paddle-tumble, soak the stirring of having a rest during this time at normal temperatures 10 hours.Wash 10 minutes throwing water metering 60kg with clear water after finishing.

5, deliming is handled: the 60kg clear water is packed in the paddle-tumble, join boric acid solution, content is: 60kg * 2%=1.2kg, JFC permeate agent 60kg * 0.2%=0.12kg soaks in the paddle-tumble of again pelt being packed into, intermittently stirs once in 30 minutes.Its operation 2 hours, finishing after 5 minutes water of compactions of clear water cleaning measure 55kg.

Select batch processing:, be divided into 2 classes substantially the size of fish specification classification on request.With 1500g to 2500g is a class, is a class more than the 2500-4000g.Obtain small dimension leather 20kg, big specification 25kg.

6, the softening processing used paddle-tumble, water is heated to 45 ℃ ± 2 ℃ after with the pelt thermal pretreatment.Again the about 30kg of another part hot water is made into pancreatin solution then, content is 30kg * 0.2%=0.06kg, NH ₄CL30kg * 2%=0.6kg prepares the back to solution and drops into pelt, constantly stirs the observing response phenomenon, checks the pelt otch, drip behind the phenolphthalein be colourless, surface is pure white, sends out slidingly, refers to trace with referring to that female extruding can keep, represent to soften and finish.To soften the pelt input of finishing again and give ready (KAL (SO) 12H earlier ₂O) in the solution, its content is 30kg * 1%=0.3kg, stops softening.Then with the leather of small dimension by soften processing with quadrat method.With stop softeningly, clear water cleans after 10-15 minute water squeezing metering size altogether, 50kg.

7, pickling is handled: the 50kg clear water is poured in the paddle-tumble, join raw materials such as NaCL, its content is: NaCL 50kg * 7%=3.5kg, HCHO 50kg * 0.5%=0.25kg JFC permeate agent, 50kg * 0.2%=0.1kg, solution prepares the back and checks pH value, pH value dropped into the 50kg leather in the solution at 1 o'clock, intermittently stirred 1 hour, soaked 12 hours, throw water measure 60kg, leather pH value 2.5.

8, pretan is handled: the 60kg clear water is poured into complex cation fatting agent content is that 60kg * 1.5%=9kg selects 12 revolutions in the rotary drum, is rotated and throw water after 30 minutes and measure 70kg.

9, chrome tanning is handled, and the 70kg clear water is packed in the rotary drum, joins basic chrome sulfate solution, content is 70kg * 17%=11.9kg, JFC permeate agent 70kg * 0.2%=0.14%, peregal 070kg * 1%=0.7kg checks that pH value is between 3.2-4.6, need not regulate pH value, pelt is dropped in the chrome liquor, select 12 revolutions that change for use, rotated 2 hours, parked 2 hours, and rotated again after 1 hour and to take out the skin of tanning and take excessively back metering 80kg of horse.

10, propose alkaline purification: the clear water of 80kg is packed in the paddle-tumble, join NaHCO ₃80kg * 1%=0.8kg, JFC permeate agent 80kg * 0.2%=0.16kg, solution stirring drops into chromed tanned leather after all soaked in the solution 10 hours at normal temperatures, threw water metering 80kg.

11, retanning is handled: the 80kg clear water is warmed in 45 ℃ of rotary drums of packing into, joins glutaraldehyde 80kg * 0.5%=0.4kg, PR-1 retanning agent 80kg * 4%=3.2kg, softener sg 80kg * 1%=0.8kg, after the solution stirring preheating leather is added in the solution.Select 12 numbers of walking around, rotated 4 hours, quiet soaking 3 hours rotated and thrown water metering 80kg in 1 hour.

12, stuffing dyeing is handled: after leather is preheating to 65 ℃, 80kg water is warmed to 60 ℃ joins moccasin fatting agent liquid 80kg * 10%=8kg, dyestuff 80kg * 1%=0.8kg, peregal 0,80kg * 1%=0.8kg, penetrating agent JFC 80kg * 0.2%=0.16kg prepares solution input leather and starts rotary drum.Select 12 numbers of walking around, work and shut down after 30 minutes, add laking agent 80kg * 1%=0.8kg, HCOOH80kg * 0.5%=0.4 throws water after rotating 30 minutes.

13, aftertreatment: seasoning equipment drying all can.

Claims (1)

1, the process for tanning of a kind of highland schizothoracin, grass carp fish-skin is characterized in that: be made of following step:

(1) the described treating processes of giving, be in rotary drum, pack into fresh fish skin and normal temperature softening water, the weight ratio of fresh fish skin and water is 1: 1, the weight of pressing water adds the salt (CNCL) of 45-5.5%, start rotary drum 1 hour, fish-skin is taken out rotary drum, remove the remaining flesh of fish of fish-skin, renew bright salt solution and cleaned in rotary drum 1 hour, salt solution is joined method with aforementioned;

(2) skimming processes, water and wet fish-skin weight are 1: 1 (following each step severe edema due to hypofunction of the spleen weight ratio is identical do not state in addition) in the dosing, by weight adding in water.The OP tensio-active agent octyl phenol of 0.4-0.6%JFC permeate agent and 2-4%, normal temperature rotated 2-3 hour in rotary drum, took out with normal-temperature water then and cleaned half an hour;

(3) the swollen process of scaling of alkali adds normal-temperature water in rotary drum, adds 3-5% in the water, white lime Ca (OH) ₂, add the 0.15-0.3%JFC permeate agent again, more than be weight ratio.The pH value of dosing is 12-14; Transfer 3-5 hour to, leather is swollen thick, and transparent feel is arranged, and takes out rotary drum, removes the squama and the reticular layer of fish-skin epidermal area, and the fish-skin clear water of scaling and finishing cleans half an hour; Used dosing is recyclable to be used 1 time again;

(4) multiple grey process is injected water in the paddle-tumble, adds talcum powder (3mgo4SiO by weight ₂H ₂O) 4%, JFC permeate agent 0.15-0.3%, pH value 12-14 drops into wet pelt, soak at room temperature 9-11 hour, per hour stir once with rod, take out pelt and cleaned 10-20 minute with clear water;

(5) deliming process is injected water in the paddle-tumble, adds 1.5-2.5% boric acid by weight, and the 0.15-0.3JFC permeate agent is put into pelt and stirred immersion 1.5-2.5 hour, cleans 10-20 minute with clear water then;

(6) softening process, with paddle-tumble water is heated to 40 ℃-45 ℃, add 0.15-0.25% industry pancreatin by weight, 1.5-3% ammonium chloride, 0.15-0.3JFC permeate agent, the wet pelt that is preheated to 41 ℃-45 ℃ dropped in the above-mentioned dosing stirred 5-10 minute, finish softening.Its determination methods is for finger extruding pelt, if can stay fingerprint and be and soften successfully.Finish the remollescent pelt and immerse alum [KAL (SO) 12H that contains weight 1% ₂O] stop in the aqueous solution softening;

(7) pickling process, water is injected 20～22 ℃ of paddle-tumble water temperatures, add 6-8% salt, 0.4-0.6% formic acid (HCHO) by weight, the 0.15-0.3%JFC permeate agent, survey PH=1, wet pelt is dropped in this dosing, stirred 1-1.5 hour, soak and finished pickling in 12-13 hour, hygrometric skin pH value is 2.5;

(8) pretan process adds entry in rotary drum, press the 1-2% weight ratio and add cationic fat liquor, and the fish-skin of packing into rotates and got final product in 25-35 minute;

(9) chrome tanning process, adding water goes in the rotary drum, add the 15-18% basic chrome sulfate by weight, the 0.15-0.3%JFC permeate agent, 0.8-1.5% peregal 0 transfers pH value between 3.2-4.6 with sodium-acetate or Sulfothiorine, the pelt of packing into, rotated at normal temperatures after 2 hours the quiet 1.5-2.5 of soaking hour, rotated again 1 hour, take out the skin of tanning and take and measure after horse crosses liquid;

(10) carry alkali, N-process, add water and in paddle-tumble, add 0.8-1.5% yellow soda ash by weight, the 0.15-0.3%JFC permeate agent, surveying pH value is 6 ± 1, and chromed tanned leather is packed in the paddle-tumble, soaks at normal temperatures 9-11 hour, intermittently stirs;

(11) retanning process is packed 40-45 ℃ of warm water in the rotary drum into, allocates glutaraldehyde [OHC. (CH into ₂) ₃CHO] 0.4-0.6%, softener sg 0.8-1.2%, with give heat in 40-45 ℃ and raw hide pack in the rotary drum, rotated 3.5-4.5 hour, quiet soaking 3 hours rotated to take out in 1 hour again and thrown water (not dripping even the leather through processing has obviously);

(12) stuffing dyeing course, to be preheated to 58-62 ℃ through the retanning raw hide earlier, 55-65 ℃, the warm water rotary drum of packing into is allocated 8-12% moccasin fatting agent (Sichuan Shi Fangshi leather retanning agent factory product), 0.8-1.2% dyestuff into, the 0.15-0.3%JFC permeate agent in warm water, 0.8-1.2 peregal 0, the skin of tanning of packing into rotates and adds 0.3-0.6% formic acid and 0.8-1.2% laking agent after 25-40 minute, rotates after 25-40 minute again and throws water;

(13) aftertreatment: drying, polishing, clean, arrangement, adopt existing known method, no longer carefully state.