CN102911395A - A method for resource recovery and utilization of waste cotton fabric - Google Patents
A method for resource recovery and utilization of waste cotton fabric Download PDFInfo
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- CN102911395A CN102911395A CN2012103889723A CN201210388972A CN102911395A CN 102911395 A CN102911395 A CN 102911395A CN 2012103889723 A CN2012103889723 A CN 2012103889723A CN 201210388972 A CN201210388972 A CN 201210388972A CN 102911395 A CN102911395 A CN 102911395A
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- phosphoric acid
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- 231100000252 nontoxic Toxicity 0.000 description 2
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- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 150000008495 β-glucosides Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
本发明涉及一种废弃棉织物的资源化回收利用方法，特别是一种将废弃涤棉混纺织物中涤纶回收及棉纤维用于生产可发酵糖的技术，属于固体废弃物资源化循环再利用领域。本发明利用浓磷酸作为溶剂，在磷酸质量分数为82-86%，固液比为1:10-1:30，反应温度为45-60℃的条件下反应2-18小时，将涤棉混纺织物中的棉纤维完全溶解，使涤纶被分离并100%回收，之后向溶液中加入水稀释溶液，使溶液中的纤维素再生，得到结晶度与聚合度都很低的再生纤维素，以适用于酶水解，经酶水解生成可发酵性糖，用于生物基产品发酵生产的碳源。废液进行蒸馏，回收浓磷酸循环使用。本发明适用于任意比例组成的涤棉混纺织物，具有操作简单，能耗较低的优点，可100%将涤纶回收，同时可回收浓磷酸降低成本，并利用棉纤维组分产出生物基能源或生物基产品。
The invention relates to a recycling method for waste cotton fabrics, in particular to a technology for recycling polyester in waste polyester-cotton blended fabrics and using cotton fibers to produce fermentable sugar, belonging to the field of solid waste resource recycling . The present invention uses concentrated phosphoric acid as a solvent, reacts for 2-18 hours under the conditions of phosphoric acid mass fraction of 82-86%, solid-to-liquid ratio of 1:10-1:30, and reaction temperature of 45-60°C, and polyester-cotton blended The cotton fiber in the fabric is completely dissolved, so that the polyester is separated and 100% recovered, and then water is added to the solution to dilute the solution to regenerate the cellulose in the solution, and the regenerated cellulose with low crystallinity and polymerization degree is obtained, which is suitable for It is used in enzymatic hydrolysis to generate fermentable sugars, which are used as carbon sources for the fermentation production of bio-based products. The waste liquid is distilled and concentrated phosphoric acid is recovered for recycling. The invention is applicable to polyester-cotton blended fabrics with any proportion, and has the advantages of simple operation and low energy consumption, can recycle 100% polyester, and can recycle concentrated phosphoric acid at the same time to reduce costs, and use cotton fiber components to produce bio-based energy or bio-based products.
Description
Technical field
The present invention relates to a kind of method of discarded cotton fabric recycling, the cotton fibre that particularly will discard in terylene-cotton blended fabric reclaims for the production of fermentable sugars, and the method for simultaneously high purity recovery terylene.
Technical background
Entered since 21 century, along with the fast development of economy, industry and population, the available natural resources tapered dosage.Simultaneously, the improper environmental pollution that causes of greenhouse gases, pollutent and disposition of solid waste of combustion of fossil fuel discharging also is on the rise.Therefore, various countries, the whole world turn to the recycling of total composition or the recycling of high added value from landfill, burning or the simple recycling disposal in past to the processing of solid waste when seeking renewable new forms of energy.
The fiber that the annual process for processing of China is produced surpasses 4,000 ten thousand tons, and wherein terylene, cotton and both BLENDED FABRIC thereof account for the over half of fiber consumption.According to the key task of " 12 " textile industry scientific-technical progress, from now on the recycling technology of Man-made Fibre and natural fiber waste textile.But owing to technology and cost reason, the discarded cotton-polyester blended fabric of the overwhelming majority still passes through landfill, burning electricity generation, even simple burning is processed.The home and abroad all is to recycle after separating with cotton component by general's terylene component wherein for the recovery of terylene, cotton and mixed fibre thereof at present.In conjunction with the component characteristics of discarded cotton fabric, for terylene, the most effectively by chemical reagent terylene hydrolysis or alcoholysis are become monomer, recycle these monomers and again make new polyster fibre; And cotton thread wherein is made of 100% Mierocrystalline cellulose, and the raw material that can be used as enzymic hydrolysis produces the monose that can ferment, so by with monose with biologically based fuels or bio-based materials such as production of ethanol from microbial fermentation, butanols, bacteria celluloses.But the crystalline texture of cotton basic fiber height changes into fermentable sugars to enzymic hydrolysis in the discarded cotton fabric very large inhibition is arranged.Therefore, recycling for cotton fibre, the method that adopts at present is again to be processed into the regeneration cotton yarn behind its opening picking, because the staple fibre that produces in the removal process is more, so it is less to be used for the amount of spinning in the cotton fibre that reclaims, cause the regeneration cotton yarn quality not high, only can be for the production of being worth lower textiles.
The fiber of different varieties in the discarded yarn fabric is separated, and is the basis of the profound recycling of discarded cotton fabric.But polyester cotton output increases year by year at present, fibre strength is enhancing trend in the cotton fabric simultaneously, the process that each component in the mixed fibre is separated is originally higher to the requirement of manpower and Technology, thereby the component Separation and Recovery of cotton fabric is more and more difficult.Document through the retrieval prior art is found, license publication number: CN102219924A, the patent of invention title: a kind of polyester cotton separates and terylene repolymerization device, the separation essence of this device, by ethylene glycol the terylene alcoholysis in the polyester cotton blending fiber to be become soluble monomer, behind the cotton component of separate solid, by polycondensation mechanism the monomer that alcoholysis obtains is regenerated terylene.This device can continuous high-efficient the separation polyester cotton in polyster fibre and cotton fibre, but the cotton fibre after proposing to separate utilize mode.And terylene is through alcoholysis and the process of polycondensation again, and cost recovery is higher, difficultly realizes that industrialization produces continuously.Textile journal, the 7th phase of 33 volumes in 2012 a kind of method that reclaims terylene and polyester cotton of having reported for work, its key step is as follows: descend reaction after 60 minutes at 185-194 ℃ dimethyl sulfoxide (DMSO) (DMSO) and textiles, terylene is dissolved by DMSO, and cotton fibre is leached from polyester liquid, reuse after washing is dry, again short chain polyester solution is distilled, recovery part DMSO reagent, remaining solid carry out polymerization in polymeric kettle, form the regenerated terylene polyester.Although the method organic efficiency is higher, can dissolve at short notice and separate polyester-cotton fabric, but DMSO reclaims comparatively difficulty fully, the residual meeting of DMSO makes the reduced viscosity of regenerated terylene, and main agents-dimethyl sulfoxide (DMSO) toxicity is higher, exists Potential environmental risk, temperature of reaction higher.The patent that another piece reclaims about polyester-cotton fabric, license publication number: CN020610005B, patent of invention title: a kind of polyster fibre or polyester piece good waste recovery recycling method, this content of the patent relates to by one or more organic solvents terylene components dissolved or alcoholysis in polyster fibre and the BLENDED FABRIC thereof, after filtering to isolate undissolved non-polyster fibre, the polyethylene terephthalate that alcoholysis is obtained or its degraded product further utilize after the processing through Distillation recovery.This method is applicable to any waste material that contains terylene, but the terylene rate of recovery can only reach more than 90%, and the reagent that relates to mostly to be toxicity stronger, the organic solvent that environmental risk is larger.Non-terylene component after the separation only can act as a fuel and be burned heat production, and added value is too low.Textile journal and for example, the 8th phase of 33 volumes in 2012 was reported a kind of separate terylene and cotton method in the discarded polyester cotton, its key step is as follows: soak 72h at normal temperature with under the clear water after blending yarn is cut into 1-2cm length, every 1.0-1.1g yarn adds 50g1-butyl-3-Methylimidazole villaumite ([BMIM] Cl) afterwards, at 130-135 ℃ of lower reaction 4h, cotton fibre is dissolved, by filtering undissolved terylene is reclaimed, afterwards to the filtrate adding distil water that filters out behind the residual yarn, make the gossypin regeneration of dissolving, and filtered and recycled.The terylene salient features that reclaims through the method does not have noticeable change, gossypin after the recovery can be used as chemical preparations or chemical feedstocks, also again spinning, make high-quality regenerated cellulose fibre, but the method separating effect is undesirable, Mierocrystalline cellulose is separated fully with terylene, reclaim terylene purity and can not reach 100%, and the amount of the needed solvent of cotton fabric of processing unit mass is larger, and complex process causes processing efficiency low higher with processing cost.
Therefore, for the huge stock number of discarded cotton fabric, to the demand of utilization of waste as resource and bio-based product development, need the environmental friendliness to discarded cotton fabric, efficient recycling mode to develop in conjunction with now.
Summary of the invention
For the problems referred to above, the object of the invention is to overcome the deficiencies in the prior art, provide that a kind of processing method is comparatively simple, environmental friendliness, discarded pure cotton fabric or polyester cotton recycling method that the product added value is higher.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
A kind of recovery method of discarded cotton fabric, its step comprises:
(1), pure cotton fabric or polyester-cotton fabric are ground into fragment as raw material, join reactor;
(2), in reactor, add strong phosphoric acid, mix with raw material, react under heating condition, wherein the reaction of strong phosphoric acid and cotton fibre generates the Mierocrystalline cellulose phosphoric acid ester, is dissolved in the reaction solution;
(3), filter, insoluble terylene component is leached, and obtains containing the filtrate of Mierocrystalline cellulose phosphoric acid ester;
(4), thin up step (3) gained filtrate, wherein the Mierocrystalline cellulose phosphoric acid ester changes into phosphoric acid and regenerated cellulose, filters to obtain regenerated cellulose, gained filtrate is concentrated, does recycle to reclaim strong phosphoric acid.
Preferably, in the step (1) pure cotton fabric or polyester-cotton fabric pulverized fragment into about 2cm.
Preferably, the strong phosphoric acid concentration of using in the step (2) is massfraction 82%-86%, more preferably 83%; Its consumption is that to make the solid-to-liquid ratio of reaction system be 1:10-1:30, more preferably 1:15.
Preferably, step (2) temperature of reaction is 45-60 ℃, more preferably 45 ℃; Reaction times is 2-18h, more preferably 12h.
Preferably, step (3) is filtered with 30 eye mesh screens.
Preferably, the amount of water of dilution usefulness is about more than 2 times of strong phosphoric acid volume in the step (4).
Preferably, be to filter with filter membrane in the step (4).
Preferably, in step (4) afterwards, also comprise an enzymolysis step, after the regenerated cellulose water is rinsed well, under the condition that adds damping fluid, add cellulase and beta-glucosidase, make regenerated cellulose generate fermentable sugars.
Wherein, the enzymolysis step temperature of reaction is 50 ℃.
Wherein, the better citric acid/sodium citrate damping fluid that is chosen as of used damping fluid.
Wherein, the usage ratio of damping fluid and regenerated fibre is less than 25:1, and the consumption of cellulase is the 15FPU/g regenerated cellulose, and the beta-glucoside enzyme dosage is the 30IU/g regenerated cellulose.
The present invention utilizes nontoxic solvent to process, with the dissolving of the cotton fibre in pure cotton fabric or the polyester cotton, and degree of crystallinity and the polymerization degree of reduction cotton fibre; Isolate simultaneously insoluble terylene component, at last the regeneration of the cotton fibre component in the solution is rear and solution separating.The Mierocrystalline cellulose of regeneration becomes fermentable sugar by enzymic hydrolysis, produces the carbon source of bioenergy or bio-based product as later stage fermentation, reaches to reduce to pollute the purpose of high efficiente callback all components.And solvent for use can be by recycling after concentrated.
The present invention is compared to prior art, and its beneficial effect comprises at least:
(1) the present invention uses strong phosphoric acid, under mild conditions, dissolve cotton fibre fully, and do not dissolve terylene, avoided the loss of terylene, insoluble terylene is separated and all recovery, and the terylene rate of recovery is up to 100%, and the terylene after reclaiming does not contain cotton fibre, capable of direct processing, save the costs such as the energy.
(2) simultaneously, the cellulose crystallity that obtains after the regeneration among the present invention is low, and specific surface area is large, has improved the efficient of enzymic hydrolysis.
(3) reagent that uses among the present invention is strong phosphoric acid, and is nontoxic, and corrodibility is little, and can concentrate rear recycling, and environmental pollution is little; The present invention carries out under lower temperature condition, and energy consumption is lower.
(4) simultaneously the Mierocrystalline cellulose after the regeneration is carried out enzymic hydrolysis and produce fermentable sugars, make that all components is fully exploited in the raw material, avoided waste.This method is applicable to discarded pure cotton fabric or the polyester-cotton fabric of arbitrary proportion blending.
Description of drawings
Fig. 1 is the schema of the inventive method.
Embodiment
In conjunction with the content of the inventive method and schema shown in Figure 1, provide following embodiment:
Example 1: the phosphoric acid of different mass mark concentration is used for discarded cotton fabric and reclaims
(1) raw material
1. polyester cotton is from the discarded jeans of 20 different brands.
2. cellulase (Celluclast1.5L) and beta-glucosidase (Novozyme 188) are bought from Novi's letter (Novozymes).
(2) method 1. is put into reactor after mixed jeans are pulverized by pulverizer, and adding massfraction in the reactor again is 82%, 83%, 86% phosphoric acid, and to keep solid-to-liquid ratio be 1:20, and making homo(io)thermism is to begin reaction after 50 ℃, and the reaction times is 18h.
2. solution filters with 30 eye mesh screens after will reacting, and will sieve undissolved terylene water and rinse well, and washing fluid and filtrate enter in the agitator.The oven dry of terylene after the flushing is stand-by.
That the cotton fibre in the raw material and strong phosphoric acid generate the Mierocrystalline cellulose phosphoric acid ester, be dissolved in the solution, and terylene do not react with strong phosphoric acid with this understanding in the reaction process cardinal principle.
3. in agitator, add 2 times to the water of phosphoric acid volume, stirred 2 minutes, make cellulose regenerated.Wherein, behind water dilution phosphoric acid, make in the situation of phosphoric acid concentration reduction, the Mierocrystalline cellulose phosphoric acid ester in the solution is reverse phosphoric acid and the regenerated cellulose of changing into again, and regenerated cellulose is insoluble to solution, separates out with floss.Solution is obtained regenerated cellulose with filter membrane or filter paper filtering, and filtrate enters the distiller distillation, and the distillation residuum is strong phosphoric acid, and reaching needs recycling after the concentration.
4. be transferred in the hydrolytic decomposition pot after the regenerated cellulose water on the filter membrane being rinsed well, add the citric acid/sodium citrate buffered soln of 50Mmol/L and the cellulase of 15FPU/g regenerated cellulose, the beta-glucosidase of 30IU/g regenerated cellulose, make the usage ratio of damping fluid and regenerated fibre less than 25:1, at 50 ℃ Water Under solution 48h, to generate fermentable sugars.Its main process comprises that cellulase becomes cellobiose and glucose to cellulose degradation, and beta-glucosidase is that cellobiose is transformed into glucose.
(3) experimental result
After measured, adopting massfraction is that the terylene rate of recovery all reaches 100% behind 82%, 83%, 86% the phosphoric acid, and the reducing sugar yield is respectively 73%, 80%, 61% in the hydrolyzed solution.
Example 2: different phosphoric acid add-ons are used for discarded cotton fabric and reclaim
(1) raw material
1. polyester cotton is from the discarded jeans of 20 different brands.
2 cellulases (Celluclast1.5L) and beta-glucosidase (Novozyme 188) are bought from Novi's letter (Novozymes).
(2) method
1. put into reactor after mixed jeans being pulverized by pulverizer, it is 1:10,1:15,1:30 that the phosphoric acid that adds again massfraction 85% in the reactor makes solid-to-liquid ratio, and making homo(io)thermism is to begin reaction after 50 ℃, and the reaction times is 7h.
2. solution filters with 30 eye mesh screens after will reacting, and will sieve undissolved terylene water and rinse well, and washing fluid and filtrate enter in the agitator.The oven dry of terylene after the flushing is stand-by.
3. in agitator, add 2 times to the water of phosphoric acid volume, stirred 2 minutes, make cellulose regenerated.Solution is obtained regenerated cellulose with membrane filtration, and filtrate enters distiller distillation, and the distillation residuum is strong phosphoric acid, and reaching needs recycling after the concentration.
4. be transferred in the hydrolytic decomposition pot after the regenerated cellulose water on the filter membrane being rinsed well, add the citric acid/sodium citrate buffered soln of 50Mmol/L and the cellulase of 15FPU/g regenerated cellulose, the beta-glucosidase of 30IU/g regenerated cellulose, make the usage ratio of damping fluid and regenerated fibre less than 25:1, at 50 ℃ Water Under solution 48h, to generate fermentable sugars.
(3) experimental result
After measured, adopting the phosphoric acid add-on is 1:10,, after the solid-to-liquid ratio of 1:15,1:30, the terylene rate of recovery is 100%, the reducing sugar yield is respectively 79%, 94%, 86% in the hydrolyzed solution.
Example 3: the differential responses temperature is used for discarded cotton fabric and reclaims
(1) raw material
1. polyester cotton is from the discarded jeans of 20 different brands.
2 cellulases (Celluclast1.5L) and beta-glucosidase (Novozyme 188) are bought from Novi's letter (Novozymes).
(2) method
1. put into reactor after mixed jeans being pulverized by pulverizer, it is 1:15 that the phosphoric acid that adds again massfraction 85% in the reactor makes solid-to-liquid ratio, and making homo(io)thermism is to begin reaction after 45,50,60 ℃, and the reaction times is 6h.
2. solution filters with 30 eye mesh screens after will reacting, and will sieve undissolved terylene water and rinse well, and washing fluid and filtrate enter in the agitator.The oven dry of terylene after the flushing is stand-by.
3. in agitator, add 2 times to the water of phosphoric acid volume, stirred 2 minutes, make cellulose regenerated.Solution is obtained regenerated cellulose with membrane filtration, and filtrate enters distiller distillation, and the distillation residuum is strong phosphoric acid, and reaching needs recycling after the concentration.
4. be transferred in the hydrolytic decomposition pot after the regenerated cellulose water on the filter membrane being rinsed well, add the citric acid/sodium citrate buffered soln of 50Mmol/L and the cellulase of 15FPU/g regenerated cellulose, the beta-glucosidase of 30IU/g regenerated cellulose, make the usage ratio of damping fluid and regenerated fibre less than 25:1, at 50 ℃ Water Under solution 48h, to generate fermentable sugars.
(3) experimental result
After measured, adopt 45,50 and 60 ℃ temperature of reaction after, the terylene rate of recovery is 100%, the reducing sugar yield is respectively 87%, 82%, 71% in the hydrolyzed solution.
The 4 differential responses times of the present invention of example are used for discarded cotton fabric and reclaim
(1) raw material
1. polyester cotton is from the discarded jeans of 20 different brands.
2 cellulases (Celluclast1.5L) and beta-glucosidase (Novozyme 188) are according to believing (Novozymes) from Novi.
(2) method
1. put into reactor after mixed jeans being pulverized by pulverizer, it is 1:20 that the phosphoric acid that adds again massfraction 85% in the reactor makes solid-to-liquid ratio, and making homo(io)thermism is to begin reaction after 50 ℃, and the reaction times is 2h, 4h, 6h, 12h and 18h.
2. will react rear solution and filter with 30 eye mesh screens, will sieve undissolved terylene water and rinse well, washing fluid and filtrate enter in the agitator.The oven dry of terylene after the flushing is stand-by.
3. in agitator, add 2 times to the water of phosphoric acid volume, stirred 2 minutes, make cellulose regenerated.Solution is obtained regenerated cellulose with membrane filtration, and filtrate enters distiller distillation, and the distillation residuum is strong phosphoric acid, and reaching needs recycling after the concentration.
4. be transferred in the hydrolytic decomposition pot after the regenerated cellulose water on the filter membrane being rinsed well, add the citric acid/sodium citrate buffered soln of 50Mmol/L and the cellulase of 15FPU/g regenerated cellulose, the beta-glucosidase of 30IU/g regenerated cellulose, make the usage ratio of damping fluid and regenerated fibre less than 25:1, at 50 ℃ Water Under solution 48h, generate fermentable sugars.
(3) experimental result
After measured, after the reaction times of employing 2h, 4h, 6h, 12h and 18h, the terylene rate of recovery is 100%, and the reducing sugar yield is respectively 70%, 72%, 80%, 70% and 65% in the hydrolyzed solution.
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| CN106674588A (en) * | 2017-01-05 | 2017-05-17 | 太原理工大学 | Method for separating and recovering waste cotton-polyester blended fabric under subcritical water condition |
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