CN101565864A - Chromium-containing leatherworking secondary waste dechromed extractive-viscose glue blending fiber and preparation method thereof - Google Patents
Chromium-containing leatherworking secondary waste dechromed extractive-viscose glue blending fiber and preparation method thereof Download PDFInfo
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- CN101565864A CN101565864A CNA200810044282XA CN200810044282A CN101565864A CN 101565864 A CN101565864 A CN 101565864A CN A200810044282X A CNA200810044282X A CN A200810044282XA CN 200810044282 A CN200810044282 A CN 200810044282A CN 101565864 A CN101565864 A CN 101565864A
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Abstract
The invention discloses a chromium-containing leatherworking secondary waste dechromed extractive-viscose glue blending fiber and a preparation method thereof. The chromium-containing leatherworking secondary waste dechromed extractive-viscose glue blending fiber is characterized by comprising the follow materials by weight portion: 10-30 portions of chromium-containing leatherworking secondary wastes and 70-90 portions of industry viscose glue. The chromium-containing leatherworking secondary wastes is taken as raw materials, and chromes is removed in an alternately complex method of an oxidation process and an acid process; then an alkaline enzyme process is utilized to obtain the extractive; the extractive is complexly matched with commercially available industrial grade viscose glue to obtain blending fabric liquid silk, and blending fibers is prepared by a wet spinning machine; and finally the chromium-containing leatherworking secondary wastes-viscose glue blending fibers are obtained through proper thermal stretch and acetalation.
Description
Technical field
The present invention relates to a kind of is main raw material to contain the chromium solid leather wastes, takes off that chromium is handled and utilizes and take off chromium extract and chemical fibre prepare blended fiber with viscose glue method.
Background technology
The history in existing over one hundred year of chrome tanning, because the advantage of chrome leather performance makes chrome tanning agent and corresponding tannage occupy leading position, except that the leather of specific use, the tannery more than 90% adopts the chrome tanning master to tan.Chrome leather scrap generally contains about 90% (the calculating with butt) of protein, Cr
2O
3Account for 3%～6%.The solid waste that annual national leather industry produces is more than 700,000 tons, and wherein containing the secondary refuse of chromium (mainly being chrome leather scrap and deburring leftover bits and pieces etc.) just has 300,000 tons more than.As seen, utilize leather bits and leftover pieces in the secondary refuse of process hides to obtain extract, and use it for and make the high product of other added value (as dress ornament fiber, gelatin etc.), and to recycle the chromium contain in the secondary refuse of chromium be the cause that an existing environment, economic benefit have social benefit again, also be simultaneously leather industry face the challenge the inevitable choice that should make.
Usually with Cr in the secondary refuse of process hides
3+The method of sloughing have dechromium methods such as acid system, alkaline process, soda acid alternative method, enzyme process and enzyme alkali combined techniques, oxidizing process (Chen Wuyong, yellow a ceremonial jade-ladle, used in libation, Lin Liang. leather leftover extracts the research [J] of collagen. Chinese leather, 2002,31 (23): 1-5).The whole bag of tricks was all once studied and was paid close attention to, and tangible advantage is arranged but different separately shortcomings is also arranged, and did not realize large-scale promotion.
Abroad, nearly 10 years of people such as Brown is handling chrome leather scrap, protein isolate product and is reclaiming and doing a lot of work aspect the research of chromium; They are at the early stage method that adopts: in 5%～6% lime solution medium, hydrolysis chrome leather scrap 4～6h under 60～65 ℃ of conditions separates obtaining the very low protolysate of chromium content, capable of using as feed and fertilizer with alkali protease; People such as Taylor has improved original method subsequently, adopt two step method (Two StepProcess) to handle chrome leather scrap, the first step adopts alkali hydrolysis method, extracts to be suitable for the gelation protein product (gelatin) that cosmetics, adhesive, printing or photographic industry etc. use; Second step adopted enzyme hydrolysis to isolate protein hydrolysate, and the Application Areas of the protein product of recovery is widened, and added value improves (Taylor M M, et al.USP:5271912,1993; Taylor M M, et al.Use of tryotec enzyme preparations in treatment ofchrome shaving.J.Am.Leather Chem.Assoc., 1999,94 (7): 268-287).Type approval test shows: this alkali, enzyme are in conjunction with the two-step process good reproducibility of handling chrome leather scrap, if it is then with practical value to reclaim enzyme, its shortcoming is that cost is higher.
People such as domestic Chen Chi adopt alkalescence to take off the dechromium method that chromium agent-oxidant is used, and it is remarkable to take off the chromium effect, take off the low (Chen Chi of collagen chrome content behind the chromium, but defend China, Ceng Rui etc. the research of chrome leather scrap oxidation dechroming [J]. leather science and engineering, 2006,16 (2): 22-25).
Viscose is an artificial fibre of realizing suitability for industrialized production the earliest, has been invented the method that makes cellulose xanthate and has been applied for patent by three Britain scientist Cross, Bevan and Beadle in 19 end of the centurys.100 for many years, viscose extremely favor of consumer owing to its comfortable taking, and its output is maximum in the cellulose fibre always.The viscose glue wide material sources are recyclability resources, and its main component is a cellulose, by the timber of occurring in nature or cotton linter through processing and obtain; Its wearability is good, and the fiber after the spinning has identical chemical constitution with natural fabric, and the fiber hygroscopicity reaches 8%～14%, can also give its new performance by processing; Viscose also can natural degradation, and itself is nontoxic, belongs to the environment friendly material.
Prior art has the following disadvantages:
1. the efficient and the cost that take off chromium are closely related, obtain to take off the chromium high efficiency and must consume expensively, have limited the popularization of dechromium method;
2. the secondary refuse of process hides does not carry out special extraction research after taking off chromium, makes extraction efficiency relatively poor, and product quality is not high and unstable.
Summary of the invention
The objective of the invention is to contain the secondary changing waste into resources utilization of chromium process hides, big pollution sources that solve leather industry improve its added value simultaneously again, its extract and viscose glue blending prepare dress ornament fiber and preparation method thereof of broad range of applicability, be characterized in that utilization contains the secondary refuse of chromium process hides and industrial viscose glue is main raw material, form through taking off prepared such as chromium, hydrolysis, blend, spinning.
The objective of the invention is to realize that wherein said raw material umber is parts by weight except that specifying by following technical measures:
Contain 10～30 parts in the secondary refuse of chromium process hides
70～90 parts of industry viscose glues
The described secondary refuse of chromium process hides that contains is meant in the process hides process that the secondary refuse of the various solids that produce comprises buffing leather bits, shaving leather bits, deburring leather bits, sheet leather bits etc. after the tanning operation.
Described industrial viscose glue is commercially available technical grade reagent.
The above-mentioned preparation method who takes off chromium extract-viscose glue blending fiber who contains the secondary refuse of chromium process hides is characterized in that: described method is to divide 9 step operations to carry out according to following technology:
(1) oxidation dechroming
Take by weighing and contain secondary refuse 10～30 weight portions of chromium process hides, add in the reactor, add 50～180 weight portion distilled water, 0.2～1.0 weight portion sodium bicarbonate, 1～5 weight portion concentration is 30% the hydrogen peroxide and the peregal of 0.04～0.12 weight portion; After stirring, again with concentration be the sodium hydroxide solution of 1mol/L to regulate pH of mixed be 9.0～9.5, continuous stirring 60～120min under 30～60 ℃ of water bath condition; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(2) acid system takes off chromium
Above-mentioned filter residue is transferred in the reactor again, added the water of 100～300 weight portions, add 0.05～0.2 weight portion oxalic acid and 0.2～1.0 weight portion sodium oxalate, stirring action 40～90min; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(3) repeat to take off chromium
Above-mentioned filter residue is transferred in the reactor again, repeated above-mentioned steps 1,2 two to four times, collect filter residue;
(4) hydrolysis is extracted
The above-mentioned filter residue that takes off behind the chromium is joined in the reactor, add 30～100 weight portion pH and be 10 NaOH-NaHCO
3Buffer solution, room temperature condition stir 40～90min down; AS 1.398 enzymes that add 0.15～0.5 weight portion, continuous stirring effect 2～6h; Mixed liquor after the above-mentioned reaction is filtered with 200 order filter clothes, collect filtrate for later use;
(5) dilution of viscose glue
Get industrial viscose glue 70～90 weight portions, add the NaOH solution dilution of 8～10 weight portion 0.1mol/L, standby;
(6) preparation of co-blended spinning liquid
The above-mentioned chromium process hides pair refuse that contains is taken off in chromium extract and the dilution viscose adding reactor, stir 30～120min and make the blend uniformity, the deaeration of filtration final vacuum is standby;
(7) preparation of coagulating bath
Prepare an amount of coagulating bath according to the coagulating basin capacity, make that wherein sodium sulfate concentration is 350 ± 10g/L, sulfuric acid concentration is 110 ± 10g/L, and zinc sulfate concentration is 10 ± 1g/L, promptly obtains coagulating bath after mixing, and is standby;
(8) preparation of blended fiber
Adopting wet-spinning frame, is coagulating bath with sodium sulphate-sulfuric acid-solution of zinc sulfate, at 30～60 ℃ of coagulation bath temperatures and 0.2～2kg/cm
2Spray silk under the nitrogen pressure condition, coagulation forming under the suitable tractive force effect obtains to contain the secondary refuse of chromium process hides and takes off chromium extract-viscose glue blending fiber semifinished product.The spinning head that adopts can but be not limited to diameter 0.08mm, 20 holes, 50 holes or 100 holes.
(9) post processing of blended fiber
The above-mentioned secondary refuse of chromium process hides that contains is taken off chromium extract-viscose glue blending fiber semifinished product after extension dries in the air 6h, and physical method is removed and is adhered to the salt of crystallization on the fiber and make fiber divide silk; After blended fiber is stretched again, acetalation and oven dry handle, can obtains to contain the secondary refuse of chromium process hides and take off chromium extract-viscose glue blending fiber.Stretching condition was when wherein the hot-stretch instrument stretched: keep 3min 100 ℃ of 10% typings that stretch down; The temperature that acetalation is bathed is 55～80 ℃, and it consists of: sulfuric acid 30～60mmol/L, sodium sulphate or ammonium sulfate 1.2～2.0mol/L, formaldehyde 20～100mmol/L or glutaraldehyde 10～80mmol/L.
Wet-spinning frame used among the present invention is produced by Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences.
Because contain in the secondary refuse of chromium process hides and have the chromium element, institute has influenced the development of leather industry to a certain extent so that its pollution control seems difficult, how to seek the suitable focus that the secondary refuse outlet of chromium process hides has become concern that contains.Adopt oxidizing process and acid system to take off chromium repeatedly, again with alkaline enzymatic hydrolysis acquisition extract, and and then with the composite spinning acquisition of industrial viscose glue blended fiber.This blended fiber has suitable physical and mechanical properties, has good biodegradable and environmental protection.Compare with the existing processes technology, the present invention has the following advantages:
(1) the secondary refuse that produces with leather industry is a main raw material, and the handling problem that has not only solved pollutant is also carried out recycling to secondary refuse, makes a silk purse out of a sow's ear; The small amounts of contamination that does not produce pollutant or generation in the processing procedure is handled easily simultaneously;
(2) contain the secondary refuse of chromium process hides and take off spinning behind chromium extract and the industrial viscose glue blending, the blended fiber of preparation has good biodegradable.
The secondary refuse of chromium that contains that the present invention is prepared takes off chromium extract-viscose glue blending fiber, and its performance satisfies application requirements:
(1) preparation dress ornament fibrous raw material;
(2) further deep processing weaves various forms of degradability fiber products.
The specific embodiment
Below by implementing that the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; and can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1:
(1) oxidation dechroming
Take by weighing and contain secondary refuse 10 weight portions of chromium process hides, add in the reactor, add 50 weight portion distilled water, 0.2 weight portion sodium bicarbonate, 1 weight portion concentration is 30% the hydrogen peroxide and the peregal of 0.04 weight portion; After stirring, again with concentration be the sodium hydroxide solution of 1mol/L to regulate pH of mixed be 9.0, continuous stirring 60min under 30 ℃ of water bath condition; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(2) acid system takes off chromium
Above-mentioned filter residue is transferred in the reactor again, added the water of 100 weight portions, add 0.05 weight portion oxalic acid and 0.2 weight portion sodium oxalate, stirring action 40min; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(3) repeat to take off chromium
Above-mentioned filter residue is transferred in the reactor again, repeated above-mentioned steps 1,2 secondaries, collect filter residue;
(4) hydrolysis is extracted
The above-mentioned filter residue that takes off behind the chromium is joined in the reactor, add 30 weight portion pH and be 10 NaOH-NaHCO
3Buffer solution, room temperature condition stir 40min down; The AS1.398 enzyme that adds 0.15 weight portion, continuous stirring effect 2h; Mixed liquor after the above-mentioned reaction is filtered with 200 order filter clothes, collect filtrate for later use;
(5) dilution of viscose glue
Get industrial viscose glue 790 weight portions, add the NaOH solution dilution of 10 weight portion 0.1mol/L, standby;
(6) preparation of co-blended spinning liquid
The above-mentioned chromium process hides pair refuse that contains is taken off in chromium extract and the dilution viscose adding reactor, stir 30min and make the blend uniformity, the deaeration of filtration final vacuum is standby;
(7) preparation of coagulating bath
Prepare an amount of coagulating bath according to the coagulating basin capacity, make that wherein sodium sulfate concentration is 350 ± 10g/L, sulfuric acid concentration is 110 ± 10g/L, and zinc sulfate concentration is 10 ± 1g/L, promptly obtains coagulating bath after mixing, and is standby;
(8) preparation of blended fiber
Adopting wet-spinning frame, is coagulating bath with sodium sulphate-sulfuric acid-solution of zinc sulfate, at 30 ℃ of coagulation bath temperatures and 0.2kg/cm
2Spray silk under the nitrogen pressure condition, coagulation forming under the suitable tractive force effect obtains to contain the secondary refuse of chromium process hides and takes off chromium extract-viscose glue blending fiber semifinished product.
(9) post processing of blended fiber
The above-mentioned secondary refuse of chromium process hides that contains is taken off chromium extract-viscose glue blending fiber semifinished product after extension dries in the air 6h, and physical method is removed and is adhered to the salt of crystallization on the fiber and make fiber divide silk; After blended fiber is stretched again, acetalation and oven dry handle, can obtains to contain the secondary refuse of chromium process hides and take off chromium extract-viscose glue blending fiber.Stretching condition was when wherein the hot-stretch instrument stretched: keep 3min 100 ℃ of 10% typings that stretch down; The temperature that acetalation is bathed is 55 ℃, and it consists of: sulfuric acid 30mmol/L, sodium sulphate 1.2mol/L, formaldehyde 20mmol/L.
Embodiment 2:
(1) oxidation dechroming
Take by weighing and contain secondary refuse 30 weight portions of chromium process hides, add in the reactor, add 180 weight portion distilled water, 1.0 weight portion sodium bicarbonates, 5 weight portion concentration are 30% the hydrogen peroxide and the peregal of 0.12 weight portion; After stirring, again with concentration be the sodium hydroxide solution of 1mol/L to regulate pH of mixed be 9.5, continuous stirring 120min under 60 ℃ of water bath condition; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(2) acid system takes off chromium
Above-mentioned filter residue is transferred in the reactor again, added the water of 300 weight portions, add 0.2 weight portion oxalic acid and 1.0 weight portion sodium oxalates, stirring action 90min; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(3) repeat to take off chromium
Above-mentioned filter residue is transferred in the reactor again, repeated above-mentioned steps 1,2 four times, collect filter residue;
(4) hydrolysis is extracted
The above-mentioned filter residue that takes off behind the chromium is joined in the reactor, add 100 weight portion pH and be 10 NaOH-NaHCO
3Buffer solution, room temperature condition stir 90min down; The AS1.398 enzyme that adds 0.5 weight portion, continuous stirring effect 6h; Mixed liquor after the above-mentioned reaction is filtered with 200 order filter clothes, collect filtrate for later use;
(5) dilution of viscose glue
Get industrial viscose glue 70 weight portions, add the NaOH solution dilution of 8 weight portion 0.1mol/L, standby;
(6) preparation of co-blended spinning liquid
The above-mentioned chromium process hides pair refuse that contains is taken off in chromium extract and the dilution viscose adding reactor, stir 30～120min and make the blend uniformity, the deaeration of filtration final vacuum is standby;
(7) preparation of coagulating bath
Prepare an amount of coagulating bath according to the coagulating basin capacity, make that wherein sodium sulfate concentration is 350 ± 10g/L, sulfuric acid concentration is 110 ± 10g/L, and zinc sulfate concentration is 10 ± 1g/L, promptly obtains coagulating bath after mixing, and is standby;
(8) preparation of blended fiber
Adopting wet-spinning frame, is coagulating bath with sodium sulphate-sulfuric acid-solution of zinc sulfate, at 60 ℃ of coagulation bath temperatures and 2kg/cm
2Spray silk under the nitrogen pressure condition, coagulation forming under the suitable tractive force effect obtains to contain the secondary refuse of chromium process hides and takes off chromium extract-viscose glue blending fiber semifinished product.
(9) post processing of blended fiber
The above-mentioned secondary refuse of chromium process hides that contains is taken off chromium extract-viscose glue blending fiber semifinished product after extension dries in the air 6h, and physical method is removed and is adhered to the salt of crystallization on the fiber and make fiber divide silk; After blended fiber is stretched again, acetalation and oven dry handle, can obtains to contain the secondary refuse of chromium process hides and take off chromium extract-viscose glue blending fiber.Stretching condition was when wherein the hot-stretch instrument stretched: keep 3min 100 ℃ of 10% typings that stretch down; The temperature that acetalation is bathed is 80 ℃, and it consists of: sulfuric acid 60mmol/L, ammonium sulfate 2.0mol/L, glutaraldehyde 80mmol/L.
Claims (2)
1. one kind contains the secondary refuse of chromium process hides and takes off chromium extract-viscose glue blending fiber, it is characterized in that with in the process hides process, the secondary refuse of the various solids that after the tanning operation, produce, comprise buffing leather bits, shaving leather bits, deburring leather bits, sheet leather bits etc. are main raw material, replace complex method by oxidation and acid system and take off chromium, utilize alkaline enzyme process to obtain extract again, again with the composite acquisition co-blended spinning of commercially available technical grade viscose glue liquid, adopt wet-spinning frame to prepare blended fiber again, contain the secondary refuse-viscose glue blending fiber of chromium process hides by suitable hot-stretch and the final acquisition of acetalation step at last.Wherein the percentage by weight of each component raw material composition is counted:
Contain 10～30 parts in the secondary refuse of chromium process hides
70～90 parts of industry viscose glues
2. as the right 1 described preparation method who contains the secondary refuse-viscose glue blending fiber of chromium process hides, it is characterized in that this method has comprised following steps:
(1) oxidation dechroming
Take by weighing and contain secondary refuse 10～30 weight portions of chromium process hides, add in the reactor, add 50～180 weight portion distilled water, 0.2～1.0 weight portion sodium bicarbonate, 1～5 weight portion concentration is 30% the hydrogen peroxide and the peregal of 0.04～0.12 weight portion; After stirring, again with concentration be the sodium hydroxide solution of 1mol/L to regulate pH of mixed be 9.0～9.5, continuous stirring 60～120min under 40 ℃ of water bath condition; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(2) acid system takes off chromium
Above-mentioned filter residue is transferred in the reactor again, added the water of 100～300 weight portions, add 0.05～0.2 weight portion oxalic acid and 0.2～1.0 weight portion sodium oxalate, stirring action 40～90min; Above-mentioned mixed liquor is filtered with 200 order filter clothes, collect filter residue;
(3) repeat to take off chromium
Above-mentioned filter residue is transferred in the reactor again, repeated above-mentioned steps 1,2 two to four times, collect filter residue;
(4) hydrolysis is extracted
The above-mentioned filter residue that takes off behind the chromium is joined in the reactor, add 30～100 weight portion pH and be 10 NaOH-NaHCO
3Buffer solution, room temperature condition stir 40～90min down; The AS1.398 enzyme that adds 0.15～0.5 weight portion, continuous stirring effect 2～6h; Mixed liquor after the above-mentioned reaction is filtered with 200 order filter clothes, collect filtrate for later use;
(5) dilution of viscose glue
Get industrial viscose glue 70～90 weight portions, add the NaOH solution dilution of 8～10 weight portion 0.1mol/L, standby;
(6) preparation of co-blended spinning liquid
Contain with above-mentioned that the secondary refuse of chromium process hides takes off the chromium extract and the dilution viscose adds in the reactor, stir 30～120min make blend evenly-cause, it is standby to filter the final vacuum deaeration;
(7) preparation of coagulating bath
Prepare an amount of coagulating bath according to the coagulating basin capacity, make that wherein sodium sulfate concentration is 350 ± 10g/L, sulfuric acid concentration is 110 ± 10g/L, and zinc sulfate concentration is 10 ± 1g/L, promptly obtains coagulating bath after mixing, and is standby;
(8) preparation of blended fiber
Adopting wet-spinning frame, is coagulating bath with sodium sulphate-sulfuric acid-solution of zinc sulfate, at 30～60 ℃ of coagulation bath temperatures and 0.2～2kg/cm
2Spray silk under the nitrogen pressure condition, coagulation forming under the suitable tractive force effect obtains to contain the secondary refuse of chromium process hides and takes off chromium extract-viscose glue blending fiber semifinished product.The spinning head that adopts can but be not limited to diameter 0.08mm, 20 holes, 50 holes or 100 holes.
(9) post processing of blended fiber
The above-mentioned secondary refuse of chromium process hides that contains is taken off chromium extract-viscose glue blending fiber semifinished product after extension dries in the air 6h, and physical method is removed and is adhered to the salt of crystallization on the fiber and make fiber divide silk; After blended fiber is stretched again, acetalation and oven dry handle, can obtains to contain the secondary refuse of chromium process hides and take off chromium extract-viscose glue blending fiber.Stretching condition was when wherein the hot-stretch instrument stretched: keep 3min 100 ℃ of 10% typings that stretch down; The temperature that acetalation is bathed is 55～80 ℃, and it consists of: sulfuric acid 30～60mmol/L, sodium sulphate or ammonium sulfate 1.2～2.0mol/L, formaldehyde 20～100mmol/L or glutaraldehyde 10～80mmol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292460A (en) * | 2021-11-15 | 2022-04-08 | 四川大学 | Method for 3D printing of personalized leather product by using chromium-containing leather scraps and waste wool |
| CN114456416A (en) * | 2022-01-13 | 2022-05-10 | 华南理工大学 | Preparation method of polyvinyl alcohol composite packaging film and polyvinyl alcohol composite packaging film |
| US11473945B2 (en) * | 2016-08-12 | 2022-10-18 | Brightsentinel Holding Ltd | Modular wireless sensing device |
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2008
- 2008-04-25 CN CNA200810044282XA patent/CN101565864A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11473945B2 (en) * | 2016-08-12 | 2022-10-18 | Brightsentinel Holding Ltd | Modular wireless sensing device |
| CN114292460A (en) * | 2021-11-15 | 2022-04-08 | 四川大学 | Method for 3D printing of personalized leather product by using chromium-containing leather scraps and waste wool |
| CN114456416A (en) * | 2022-01-13 | 2022-05-10 | 华南理工大学 | Preparation method of polyvinyl alcohol composite packaging film and polyvinyl alcohol composite packaging film |
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Open date: 20091028 |