JP4947369B2 - Cotton recovered from waste materials containing cotton - Google Patents
Cotton recovered from waste materials containing cotton Download PDFInfo
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- JP4947369B2 JP4947369B2 JP2007205438A JP2007205438A JP4947369B2 JP 4947369 B2 JP4947369 B2 JP 4947369B2 JP 2007205438 A JP2007205438 A JP 2007205438A JP 2007205438 A JP2007205438 A JP 2007205438A JP 4947369 B2 JP4947369 B2 JP 4947369B2
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- 229920000742 Cotton Polymers 0.000 title claims description 126
- 239000002699 waste material Substances 0.000 title description 22
- 239000002245 particle Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000010784 textile waste Substances 0.000 claims 6
- 239000000835 fiber Substances 0.000 description 18
- 238000011084 recovery Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000013001 point bending Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000000855 fermentation Methods 0.000 description 8
- 230000004151 fermentation Effects 0.000 description 8
- 239000012779 reinforcing material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000538 analytical sample Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
本発明は、綿を含む廃棄材料から回収された耐熱性・成形性に優れた綿に関する。 The present invention relates to cotton excellent in heat resistance and moldability recovered from waste materials containing cotton.
綿は現在、衣料品の原料として広く大量に用いられている。しかしながら、綿は単独で用いられるばかりではなく、合成高分子などと一緒に加工品とされることが多い。例えば綿とポリエステル等の混紡織・編物などとして広く利用されている。これらの衣料品の縫製過程における裁断屑や端切れ、及び古着などが毎年大量に発生しているが、セルロース系高分子と合成高分子等との簡便な選別技術が無いため、これらの加工品を有効にリサイクルする上で大きな問題になっている。 Cotton is now widely used in large quantities as a raw material for clothing. However, cotton is not only used alone, but is often processed into products with synthetic polymers. For example, it is widely used as a mixed woven / knitted fabric of cotton and polyester. A large amount of cutting scraps, scraps, and used clothing are generated every year in the sewing process of these garments, but since there is no simple sorting technology between cellulosic polymers and synthetic polymers, these processed products are It is a big problem in recycling effectively.
現在これらの加工品の多くの場合、最終的には細かく裁断した後に土中への埋め立てや焼却処分などがなされているが、より効果的な綿のリサイクルにより高度の利用が可能となれば持続的な社会の発展に必要な、省資源、省エネルギー、地球温暖化防止技術となる。一方、本発明者らは、綿を含む廃棄材料を酸で加水分解処理することで綿が粒子化し、繊維形状を保つPETと形態差を利用して分離・回収できることを見出している(特許文献1,2)。また回収された綿は、粒子化され、非常に結晶性が高く、かつ高い弾性率を有することから繊維補強材料、或いはアセテート等のセルロース誘導体として有効に利用できる可能性がある。更に加水分解処理された綿は、DP（重合度）が数百オーダーまで低下するので、発酵用原料としての利用可能性もある。
しかしながら得られた回収綿は耐熱性が低く、溶融樹脂とのコンポジット工程において熱分解が起こり補強用材料としての特徴を発揮できないという問題があった。更に回収綿の粒径によっては、溶融樹脂に均一に分散されず目的とするコンポジットの物性が得られない、また発酵用原料として利用するときに発酵速度を制御できないという問題があった。
Currently, many of these processed products are finally finely cut and then landfilled or incinerated, but will continue if advanced utilization becomes possible through more effective cotton recycling. It becomes a resource saving, energy saving, and global warming prevention technology necessary for the development of a healthy society. On the other hand, the present inventors have found that the waste material containing cotton is hydrolyzed with an acid to form cotton particles, which can be separated and recovered using PET and shape differences that maintain the fiber shape (Patent Literature). 1,2). Further, since the recovered cotton is granulated, has a very high crystallinity, and has a high elastic modulus, there is a possibility that it can be effectively used as a fiber reinforcing material or a cellulose derivative such as acetate. Furthermore, since the hydrolyzed cotton has a DP (degree of polymerization) of several hundreds of orders, it can be used as a raw material for fermentation.
However, the obtained recovered cotton has low heat resistance, and there is a problem that thermal decomposition occurs in the composite process with the molten resin and the characteristic as a reinforcing material cannot be exhibited. Furthermore, depending on the particle size of the recovered cotton, there is a problem that the desired composite physical properties cannot be obtained because the dispersed cotton is not uniformly dispersed, and the fermentation rate cannot be controlled when used as a fermentation raw material.
本発明の目的は、綿を含む廃棄材料から回収された耐熱性、成形性に優れた綿を提供することにある。また本発明の別の目的は、回収綿を廃棄材料から効率的に分離・回収する方法を提供することにある。 The objective of this invention is providing the cotton excellent in the heat resistance and the moldability collect | recovered from the waste material containing cotton. Another object of the present invention is to provide a method for efficiently separating and recovering recovered cotton from waste materials.
本発明者らは、前記目的を達成するために鋭意検討した結果、特定濃度のHCl水溶液で加水分解処理することにより、耐熱性に優れ、粒径が一定範囲に制御された綿を効率的に分離・回収できることを実験的に見出し、この知見に基づいて本発明を完成した。
すなわち、本発明は綿を含む廃棄材料から回収された綿であって、酸素雰囲気下、250℃で30分間保持した時の減量率1.5wt%以下で、平均粒径0.01〜30μmであることを特徴とする綿を含む廃棄材料から回収された綿である。
As a result of intensive investigations to achieve the above-mentioned object, the present inventors have efficiently performed cotton having excellent heat resistance and particle size controlled within a certain range by hydrolyzing with an aqueous HCl solution having a specific concentration. It was experimentally found that separation and recovery were possible, and the present invention was completed based on this finding.
That is, the present invention is a cotton recovered from waste materials including cotton, and has a weight loss rate of 1.5 wt% or less and an average particle size of 0.01 to 30 μm when held at 250 ° C. for 30 minutes in an oxygen atmosphere. Cotton recovered from waste material containing the characteristic cotton.
本発明の回収綿は、繊維補強用材料、発酵原料、誘導体原料に有効に利用することができる。また効果的な綿のリサイクルにより高度の利用が可能となれば持続的な社会の発展に必要な、省資源、省エネルギー、地球温暖化防止技術と多いに寄与するものである。 The recovered cotton of the present invention can be effectively used as a fiber reinforcing material, fermentation raw material, and derivative raw material. In addition, if advanced utilization becomes possible by effective cotton recycling, it will contribute to many resources and energy saving and global warming prevention technologies necessary for sustainable social development.
本発明の対象となる綿を含む廃棄材料とは、綿混率が10〜80wt%の非加工品や加工品が包含される。
非加工品としては、綿を含む植物などが例示される。加工品としては、綿を含む繊維製品や紙製品が考えられるが、これらに限定されるものではなく綿を含む成形品であればよい。本発明で好ましく用いられる加工品は、綿とポリエステルの混紡繊維、及び／又は混紡繊維製品である。
繊維補強材料は、ナイロンやポリ乳酸等の溶融樹脂とコンポジットを形成するために押し出し機内で長時間高温状態にさらされている。そのため、回収綿が繊維補強材料としての特性を発揮するためには、上記の条件下でも、分解ガスの発生や重合度の低下、弾性率の低下が起こらないことが必要である。
本発明の回収綿の硫黄元素含有量は500ppm以下であることが必要である。硫黄元素含
有量が500ppmを超えると回収綿の耐熱性や弾性率が低下し、繊維補強材料として利用す
ることができない。好ましくは300ppm以下で、更に好ましくは50ppm以下である。
本発明の回収締の重合度DPは50〜500である。回収綿の重合度DPが50を下回ると耐
熱性が著しく低下する。また酸加水分解法で500をこえることは困難である。繊維補強材
料としての特性向上という観点から、好ましくは重合度DPが100〜300である。
The waste material containing cotton, which is the subject of the present invention, includes non-processed products and processed products having a cotton mixing ratio of 10 to 80 wt%.
Examples of non-processed products include plants containing cotton. The processed product may be a fiber product or paper product containing cotton, but is not limited thereto, and may be a molded product containing cotton. The processed article preferably used in the present invention is a blended fiber of cotton and polyester and / or a blended fiber product.
The fiber reinforced material is exposed to a high temperature state for a long time in an extruder to form a composite with a molten resin such as nylon or polylactic acid. Therefore, in order for the recovered cotton to exhibit the characteristics as a fiber reinforcing material, it is necessary that the generation of decomposition gas, the degree of polymerization, and the elastic modulus do not occur even under the above conditions.
The sulfur content of the recovered cotton of the present invention is required to be 500 ppm or less. If the sulfur element content exceeds 500 ppm, the heat resistance and elastic modulus of the recovered cotton will decrease, and it cannot be used as a fiber reinforcement material. Preferably it is 300 ppm or less, More preferably, it is 50 ppm or less.
The polymerization degree DP of the recovery fastening of the present invention is 50 to 500. When the degree of polymerization DP of the recovered cotton is less than 50, the heat resistance is significantly reduced. It is difficult to exceed 500 by acid hydrolysis. From the viewpoint of improving the properties as a fiber reinforcing material, the polymerization degree DP is preferably 100 to 300.
本発明の綿を含む廃棄材料から回収された綿は酸素雰囲気下、250℃で30分間保持した
時の減量率が1.5wt％以下である必要がある。本発明の回収綿は、酸素雰囲気下、250℃で30分間保持した時の減量率が1.5wt％以下であり、押し出し機内での熱分解が起きない。
減量率が1.5wt％をこえる回収綿を繊維補強材料として利用すると、成形工程で、熱分解が起こり、分解ガスの発生、重合度の低下、弾性率の低下などが起こり繊維補強材料としての特性を発揮することができない。好ましくは、減量率1.3wt％以下で、さらに好ましくは1.0wt％以下である。
また本発明の回収綿は、平均粒径0.01〜30μｍである必要がある。回収綿の平均粒径が30μｍをこえると、コンポジット成形工程において溶融樹脂と混ざりにくく、回収綿が均一に分散されたコンポジットが得られない。更に発酵用原料として利用しても、発酵速度を制御できない。繊維補強材料としての回収綿の溶融樹脂中における分散性向上の観点から、好ましくは、平均粒径0.01〜25μｍ、更に好ましくは0.01〜15μｍである。
本発明の回収綿は、綿の含有量が90wt％以上であることが、補強繊維材料としての特性を発揮するためには好ましい。なお10％未満であってかつ回収綿の耐熱性を阻害しない範囲であればPETや金属くず等の不純物を含有していても良い。好ましくは95wt％以上で、更に好ましくは99wt％以上である。
The cotton recovered from the waste material containing the cotton of the present invention needs to have a weight loss rate of 1.5 wt% or less when kept at 250 ° C. for 30 minutes in an oxygen atmosphere. The recovered cotton of the present invention has a weight loss rate of 1.5 wt% or less when held at 250 ° C. for 30 minutes in an oxygen atmosphere, and thermal decomposition does not occur in the extruder.
When recovered cotton with a weight loss rate exceeding 1.5 wt% is used as a fiber reinforcement material, thermal decomposition occurs in the molding process, generating decomposition gas, lowering the degree of polymerization, lowering the elastic modulus, etc. Can not demonstrate. Preferably, the weight loss rate is 1.3 wt% or less, more preferably 1.0 wt% or less.
The recovered cotton of the present invention needs to have an average particle size of 0.01 to 30 μm. When the average particle size of the recovered cotton exceeds 30 μm, it is difficult to mix with the molten resin in the composite molding process, and a composite in which the recovered cotton is uniformly dispersed cannot be obtained. Furthermore, even if it is used as a fermentation raw material, the fermentation rate cannot be controlled. From the viewpoint of improving the dispersibility of the recovered cotton as a fiber reinforcing material in the molten resin, the average particle size is preferably 0.01 to 25 μm, more preferably 0.01 to 15 μm.
The recovered cotton of the present invention preferably has a cotton content of 90 wt% or more in order to exhibit properties as a reinforcing fiber material. In addition, it may contain impurities such as PET and scrap metal as long as it is less than 10% and does not impair the heat resistance of the recovered cotton. Preferably it is 95 wt% or more, More preferably, it is 99 wt% or more.
綿を含む廃棄材料から綿を分離・回収する方法についてステップごとに説明する。
(a) 綿を含む廃棄材料を1〜100mm角に裁断する工程
投入する廃棄材料はロータリーカッターなどによる粉砕機で1〜100mm角に裁断する。100ｍｍ角をこえると加水分解された綿を機械的に分離することが困難である。また1mm角未満では切断粉砕機に何度も繰り返してかける必要があり、作業効率が悪くなる。好ましくは、2〜50mm角で、より好ましくは5〜30mm角に裁断する。
(b) 0.05〜1wt%のHCl水溶液に(a)で得られた裁断物を0.1〜40wt%で投入する工程
(a)で得られた裁断物を、HCl水溶液で処理する必要がある。このHCl水溶液による加水分解の工程を経てないと、例え請求項3の(g)の工程を行ったとしても請求項1記載の平均粒径0.01〜30μmの条件を満たすことはできない。
A method for separating and collecting cotton from waste material containing cotton will be described step by step.
(a) Cutting waste material including cotton into 1 to 100 mm square Waste material to be input is cut into 1 to 100 mm square with a pulverizer such as a rotary cutter. If it exceeds 100 mm square, it is difficult to mechanically separate the hydrolyzed cotton. On the other hand, if it is less than 1 mm square, it is necessary to repeatedly apply it to the cutting and grinding machine, resulting in poor work efficiency. Preferably, it is cut into 2 to 50 mm square, more preferably 5 to 30 mm square.
(b) A step of adding the cut material obtained in (a) to 0.05 to 1 wt% HCl aqueous solution at 0.1 to 40 wt%
It is necessary to treat the cut product obtained in (a) with an aqueous HCl solution. Unless the hydrolysis step using this aqueous HCl solution is performed, even if the step (g) of claim 3 is performed, the condition of the average particle size of 0.01 to 30 μm described in claim 1 cannot be satisfied.
綿の加水分解反応は、H2SO4水溶液中でも進行するが、H2SO4水溶液処理で回収された綿は耐熱性が著しく低下し、繊維補強用材料或いはセルロース誘導体原料として有効に利用することができない。処理に用いるHCl水溶液の濃度は0.05〜1wt%である。処理濃度が0.05wt%未満のHCl水溶液である場合、加水分解が進行せず、綿の回収率が著しく低下する。一方、1wt%をこえるHCl水溶液である場合、回収された綿の耐熱性が低下すると同時に、綿が水溶性のセルビオースまで分解が進行し、回収率が低下する。好ましくは0.1〜1wt%、更に好ましくは0.3〜0.6wt%のHCl水溶液を用いる。
また処理濃度は0.1〜40wt%である。処理濃度が0.1wt%未満であると、生産効率が著しく低下する。40wt%をこえると加水分解処理が部分的にしか行われず、分離・回収効率が低下する。好ましくは1〜30wt%、更に好ましくは5〜20wt%である。
Hydrolysis of cotton, can proceed even H 2 SO 4 aqueous solution, the cotton recovered in aqueous H 2 SO 4 treatment heat resistance is significantly reduced, effectively used as the fiber reinforcing material or a cellulose derivative material I can't. The concentration of the aqueous HCl solution used for the treatment is 0.05 to 1 wt%. In the case of an aqueous HCl solution having a treatment concentration of less than 0.05 wt%, hydrolysis does not proceed and the cotton recovery rate is significantly reduced. On the other hand, when the HCl aqueous solution exceeds 1 wt%, the heat resistance of the recovered cotton is lowered, and at the same time, the cotton is decomposed to water-soluble cellobiose, and the recovery rate is lowered. Preferably 0.1 to 1 wt%, more preferably 0.3 to 0.6 wt% HCl aqueous solution is used.
The treatment concentration is 0.1 to 40 wt%. When the treatment concentration is less than 0.1 wt%, the production efficiency is significantly reduced. If it exceeds 40 wt%, the hydrolysis process is only partially performed, and the separation / recovery efficiency decreases. Preferably it is 1-30 wt%, More preferably, it is 5-20 wt%.
(c) 100〜150℃で10分〜4時間処理する工程
廃棄材料をHCl水溶液に投入してから、100〜150℃で、10分〜4時間処理する。なお、ここでの処理温度100〜150℃とは反応槽内の温度をいう。また処理時間は、処理温度に達したところから、カウントする。処理温度が100℃もしくは処理時間が10分未満であると、加水分解が進行せず回収率が下がり、また回収綿の粒径が30μmをこえる。処理温度が150℃をこえる、もしくは4時間をこえると、回収綿の耐熱性が低下し、また水溶性のセルビオースまで分解が進行し、その結果、回収率が低下する。好ましくは、処理温度が110〜145℃で、処理時間が30分〜3時間で、更に好ましくは120〜140℃で、40分〜2時間である。
(c) Step of treating at 100 to 150 ° C. for 10 minutes to 4 hours After throwing the waste material into an aqueous HCl solution, treatment is carried out at 100 to 150 ° C. for 10 minutes to 4 hours. In addition, the processing temperature 100-150 degreeC here means the temperature in a reaction tank. The processing time is counted when the processing temperature is reached. When the treatment temperature is 100 ° C. or the treatment time is less than 10 minutes, hydrolysis does not proceed and the recovery rate decreases, and the particle size of the recovered cotton exceeds 30 μm. If the treatment temperature exceeds 150 ° C or exceeds 4 hours, the heat resistance of the recovered cotton decreases, and the decomposition progresses to water-soluble cellobiose. As a result, the recovery rate decreases. Preferably, the treatment temperature is 110 to 145 ° C. and the treatment time is 30 minutes to 3 hours, more preferably 120 to 140 ° C. and 40 minutes to 2 hours.
(d) 80℃以下まで冷却後、溶液中のpHを6.5〜8.2になるまで中和し、1〜20wt%のスラリー濃度になるように水を投入する工程
処理した後の廃棄材料を80℃以下まで冷却後、溶液中のpHが6.5〜8.2になるまで中和する必要がある。pH6.5〜8.2の範囲に中和することで綿の加水分解の進行を停止させて、回収綿の耐熱性、粒径を一定範囲にコントロールできる。好ましくは、pHが6.8〜8.0で、更に好ましくは、pHが6.9〜7.5である。中和剤としては、特に限定はないがKOH、NaOH、NaHCO3、アンモニア等が挙げられる。また中和した後、1〜20wt%のスラリー濃度になるように水を投入する。20wt％をこえるスラリー濃度であれば、水量が少なすぎて、攪拌による分離効率が悪くなり、回収率が低下する。1wt%未満のスラリー濃度では、大量の水を使用し水かさが増えるため、作業効率、攪拌効率ともに下がる。好ましくは1〜15wt%で、更に好ましくは4〜10wt%のスラリー濃度になるように水を投入する。
(d) Step of cooling to 80 ° C. or lower, neutralizing the solution to pH 6.5 to 8.2, and adding water so that the slurry concentration becomes 1 to 20 wt%. After cooling to below, it is necessary to neutralize until the pH in the solution is 6.5-8.2. By neutralizing to pH 6.5-8.2, the progress of hydrolysis of cotton can be stopped, and the heat resistance and particle size of recovered cotton can be controlled within a certain range. The pH is preferably 6.8 to 8.0, and more preferably 6.9 to 7.5. The neutralizing agent is not particularly limited, and examples thereof include KOH, NaOH, NaHCO 3 , and ammonia. After neutralization, water is added so that the slurry concentration becomes 1 to 20 wt%. If the slurry concentration exceeds 20 wt%, the amount of water is too small, the separation efficiency by stirring deteriorates, and the recovery rate decreases. If the slurry concentration is less than 1 wt%, both the working efficiency and the agitation efficiency will decrease because a large amount of water is used and the water volume increases. Water is added so that the slurry concentration is preferably 1 to 15 wt%, more preferably 4 to 10 wt%.
(e) 二軸の攪拌翼を有する反応機で、50〜500rpmで10分〜5時間攪拌し、圧搾する工程
綿を分離・回収するために残留物を二軸の攪拌翼を有する反応機で、50〜500rpmで1
0分〜5時間攪拌した後、圧搾することが適当である。圧搾することで廃棄材料に付着している回収綿を分離し、その後、ろ過操作を行うことで回収綿を得ることができる。もし50rpm以下の回転や圧搾をしない場合、廃棄材料に付着した粒子状の回収綿を分離できず、回収率が下がってしまう。好ましくは200〜400rpmで、更に好ましくは250〜350rpmで10分〜5時間攪拌し、(d)及び(f)の工程を2〜5回繰り返すことである。
(f) (e)で回収した綿繊維を105〜120℃で10分〜5時間で乾燥する工程
回収した綿繊維は、水等の溶媒を含んでいるために、105〜120℃で10分〜5時間で加熱乾燥することが必要である。105℃未満であれば、水を完全に除去できず回収綿の貯蔵中に腐敗が進む。120℃をこえても、乾燥時間に変化はなく、エネルギーがかかるだけで不経済である。
(e) Step of stirring and squeezing at 50 to 500 rpm for 10 minutes to 5 hours in a reactor having biaxial stirring blades In a reactor having biaxial stirring blades, the residue is separated and recovered in order to separate and collect cotton. 1 at 50-500rpm
It is appropriate to squeeze after stirring for 0 minutes to 5 hours. The collected cotton adhering to the waste material is separated by squeezing, and then the collected cotton can be obtained by performing a filtration operation. If rotation and compression are not performed at 50 rpm or less, the particulate recovered cotton attached to the waste material cannot be separated, and the recovery rate decreases. The stirring is preferably performed at 200 to 400 rpm, more preferably 250 to 350 rpm for 10 minutes to 5 hours, and the steps (d) and (f) are repeated 2 to 5 times.
(f) A step of drying the cotton fiber collected in (e) at 105 to 120 ° C. for 10 minutes to 5 hours. The collected cotton fiber contains a solvent such as water, and therefore it is 10 minutes at 105 to 120 ° C. Heat drying in ~ 5 hours is necessary. If it is less than 105 degreeC, water cannot be removed completely and decay will advance during storage of collection | recovery cotton. Even if it exceeds 120 ° C, there is no change in the drying time, and it is uneconomical because it only takes energy.
(g) (f)で得られた回収綿を粉砕する工程
(f)で得られた回収綿を更に微粒子化するという観点で、回収綿を粉砕することが好ましい。粉砕機にかけることで0.01〜1μmの均一な微粒子が得られる。
本発明の回収綿は、繊維補強用材料、発酵原料、誘導体原料に有効に利用することができる。また効果的な綿のリサイクルにより高度の利用が可能となれば持続的な社会の発展
に必要な、省資源、省エネルギー、地球温暖化防止技術と多いに寄与するものである。
(g) A step of pulverizing the recovered cotton obtained in (f)
From the viewpoint of further micronizing the recovered cotton obtained in (f), the recovered cotton is preferably pulverized. By applying to a pulverizer, uniform fine particles of 0.01 to 1 μm are obtained.
The recovered cotton of the present invention can be effectively used as a fiber reinforcing material, fermentation raw material, and derivative raw material. In addition, if advanced utilization becomes possible by effective cotton recycling, it will contribute to many resources and energy saving and global warming prevention technologies necessary for sustainable social development.
以下、実施例を挙げて本発明より詳細に説明するが、いうまでもなく本発明は実施例などにより何ら限定されるものでない。なお、実施例中の主な測定値は以下の方法で測定した。
(1)回収綿の回収率
回収率は、廃棄材料に含まれている綿の割合をa、回収量をb、投入した廃棄材料の重量w0とした時の回収率yを次式により求めた。
y=b／(a×w0)×100
(2)回収綿の平均粒径の測定
ベックマンコールター社製のレーザー回折-散乱法平均粒径測定装置（機種：LSI3320）を用い、回収綿を水に懸濁させて流し、測定した。
(3)回収綿の硫黄元素含有量の測定
得られた回収綿を発光分析装置(ICP)を用いて硫黄の分析を行い、硫黄元素含有量を求めた。
EXAMPLES Hereinafter, although an Example is given and it demonstrates in detail from this invention, of course, this invention is not limited at all by an Example etc. The main measurement values in the examples were measured by the following methods.
(1) Recovery rate of recovered cotton The recovery rate is obtained from the following equation using the following equation as the recovery rate y, where the percentage of cotton contained in the waste material is a, the recovery amount is b, and the weight of the waste material input is w 0 It was.
y = b / (a × w 0 ) × 100
(2) Measurement of average particle diameter of recovered cotton Using a laser diffraction-scattering method average particle diameter measuring device (model: LSI3320) manufactured by Beckman Coulter, the recovered cotton was suspended in water and measured.
(3) Measurement of sulfur element content of recovered cotton The obtained recovered cotton was analyzed for sulfur using an emission analyzer (ICP) to determine the elemental sulfur content.
(4)回収綿の重合度の測定
重合度DPは銅エチレンジアミン法を用いてLAUDA社製の動粘土測定装置（PROLINE PVL24）を用いて液の流下速度を測定した。
セルロースを溶解させた銅エチレンジアミン溶液の流下時間(t(秒))と無添加同溶液の流下時間(t0(秒))から、相対粘度ηrを求める。
ηr = t／t0
次に、それぞれの濃度における比粘度ηspを以下の式より求める。
ηsp =ηr−1
比粘度を次式に挿入して固有粘度[η]を求める。
[η]＝ηsp／100×c×(1+0.28×ηsp) (c:試料濃度)
以下の式より粘度平均重合度DPを求めた。
DP = 175×[η]
分析試料は以下のようにして調整した。セルロース1gに純水20mlを加え30分間攪拌した後、銅エチレンジアミン溶液（1M銅、2Mエチレンジアミン）20ml加え、30分間攪拌して、分析試料とした（非特許文献１）。
非特許文献１ 木材化学, ユニ出版, p.40, (1983)
(4) Measurement of degree of polymerization of recovered cotton The degree of polymerization DP was measured using a copper ethylenediamine method, and the flow rate of the liquid was measured using a dynamic clay measuring device (PROLINE PVL24) manufactured by LAUDA.
The relative viscosity η r is determined from the flow time (t (second)) of the copper ethylenediamine solution in which cellulose is dissolved and the flow time (t 0 (second)) of the additive-free solution.
η r = t / t 0
Next, the specific viscosity η sp at each concentration is obtained from the following equation.
η sp = η r −1
The intrinsic viscosity [η] is obtained by inserting the specific viscosity into the following equation.
[η] = η sp /100×c×(1+0.28×η sp ) (c: sample concentration)
The viscosity average polymerization degree DP was determined from the following formula.
DP = 175 × [η]
The analytical sample was prepared as follows. After adding 20 ml of pure water to 1 g of cellulose and stirring for 30 minutes, 20 ml of copper ethylenediamine solution (1M copper, 2M ethylenediamine) was added and stirred for 30 minutes to obtain an analytical sample (Non-patent Document 1).
Non-Patent Document 1 Wood Chemistry, Unipublishing, p.40, (1983)
(5)回収綿の耐熱性の測定
エスアイアイナノテクノロジー社製のTG／DTA（機種：TMA／SS120U）を用いて、空気200ml／minを流しながら、室温から50℃／minで250℃まで昇温して、250℃で30分間ホールドした時の質量減量率を評価した。
(6)回収綿の含有率の測定
回収綿1gをヘキサフロロイソプロピルアルコール（HFIP）100mlと混合し、室温で1時間攪拌してから、一晩放置した。溶液をろ過した後、沈殿物を150mlのHFIPで洗浄してから、メタノール150mlで再度洗浄した。残綿を105℃で2時間乾燥させた後、デシケーター内に30分間放置し、室温にした。この時の綿の回収量をw1、処理前の量をw2とした時、次式により回収綿の含有率xを求める。
x=(w2−w1)／w2×100
(7)3点曲げ剛性、破断強度の測定
射出成形品を23℃、50%相対湿度、24時間の状態調節し、JIS K 7203に準拠して3点曲げ剛性と破断強度を測定した。
(8)射出成形品を目視にて観察し、繊維の凝集体の有無における均一性を評価した。
(5) Measurement of heat resistance of recovered cotton Using TG / DTA (model: TMA / SS120U) manufactured by SII Nano Technology Inc., air is flown from room temperature to 250 ° C at 50 ° C / min while flowing air at 200 ml / min. The mass loss rate when heated and held at 250 ° C. for 30 minutes was evaluated.
(6) Measurement of content of recovered cotton 1 g of recovered cotton was mixed with 100 ml of hexafluoroisopropyl alcohol (HFIP), stirred at room temperature for 1 hour, and left overnight. After filtering the solution, the precipitate was washed with 150 ml HFIP and then again with 150 ml methanol. The remaining cotton was dried at 105 ° C. for 2 hours and then left in a desiccator for 30 minutes to reach room temperature. When the amount of collected cotton at this time is w 1 and the amount before treatment is w 2 , the content x of the collected cotton is obtained by the following formula.
x = (w 2 −w 1 ) / w 2 × 100
(7) Measurement of three-point bending rigidity and breaking strength The injection molded product was conditioned at 23 ° C, 50% relative humidity and 24 hours, and the three-point bending rigidity and breaking strength were measured according to JIS K 7203.
(8) The injection-molded product was visually observed to evaluate the uniformity in the presence or absence of fiber aggregates.
〔実施例１〕
綿を31wt%含む綿／PET混の廃棄材料を切断粉砕機で50mm角に粉砕して、テフロン（登録商標）コーティングを施したオートクレーブに粉砕した廃棄材料1.0g投入し、0.4wt%のHCl水溶液100mlを加えた。密栓してから、130℃に温度設定し、室温から10℃／minで昇温して、130℃になったところから1時間カウントした。その後、室温まで冷却し、溶液中のpHが7.2になるまで0.5wt%水酸化ナトリウム水溶液を加えて中和した後、純水を100ml加えた。この後、廃棄材料を取り出し、二軸の攪拌翼を有する反応機で300rpmで一時間攪拌した後、1メッシュの金網でろ過し、更に圧搾してから水洗する。ここで網上に残っている残渣がPETで、水と共に洗い落ちたのが回収綿である。この圧搾、水洗の一連の操作を5回繰り返してPETにからみついた回収綿を完全に洗い流した。回収綿を105℃で4時間かけて乾燥させた後、粉砕機を用いて粉砕した。回収量は306mgで回収率は99%だった。得られた回収綿の物性を表1に示す。なお得られた回収綿は、本発明の範囲に相当するものであった。
[Example 1]
Cotton / PET mixed waste material containing 31wt% cotton is crushed to 50mm square with a cutting pulverizer, and 1.0g of waste material pulverized into an autoclave coated with Teflon (registered trademark), 0.4wt% HCl aqueous solution 100 ml was added. After sealing, the temperature was set to 130 ° C., the temperature was raised from room temperature at 10 ° C./min, and counted from 1 hour when the temperature reached 130 ° C. Thereafter, the mixture was cooled to room temperature, neutralized by adding a 0.5 wt% aqueous sodium hydroxide solution until the pH in the solution reached 7.2, and then 100 ml of pure water was added. Thereafter, the waste material is taken out, stirred at 300 rpm for 1 hour in a reactor having a biaxial stirring blade, filtered through a 1-mesh wire mesh, further squeezed and then washed with water. Here, the residue left on the net is PET, and the recovered cotton is washed away with water. The series of operations of pressing and rinsing was repeated 5 times to completely wash away the collected cotton entangled in the PET. The recovered cotton was dried at 105 ° C. for 4 hours and then pulverized using a pulverizer. The recovered amount was 306 mg and the recovery rate was 99%. Table 1 shows the physical properties of the obtained recovered cotton. The recovered cotton obtained corresponded to the scope of the present invention.
〔実施例2〕
実施例1の回収綿を、ホソカワミクロン社製の粉砕機(機種：ACMパルペライザ)を用いて、3回微粉砕を行った。得られた回収綿の平均粒径を表1に記す。なお得られた回収綿は、本発明の範囲に相当するものだった。
〔実施例3〜10〕
実施例1の綿を含む廃棄材料を用いて、表1に示した条件で、回収綿を得た。得られた回収綿の回収率及び物性は表1に記す。いずれの回収綿も本発明の範囲に相当するものであった。
(Example 2)
The recovered cotton of Example 1 was finely pulverized three times using a pulverizer (model: ACM pulperizer) manufactured by Hosokawa Micron. The average particle diameter of the obtained recovered cotton is shown in Table 1. The recovered cotton obtained corresponds to the scope of the present invention.
(Examples 3 to 10)
Using the waste material containing the cotton of Example 1, recovered cotton was obtained under the conditions shown in Table 1. Table 1 shows the recovery rate and physical properties of the recovered cotton. Any recovered cotton corresponded to the scope of the present invention.
〔比較例1、2〕
実施例1の綿を含む廃棄材料と硫酸を用いてそれぞれ表1の条件で、回収綿を得ようとした。得られた回収綿の回収率及び物性は表1に記す。回収綿は得られたものの、高温処理後の質量減量率、硫黄元素含有量が高く本発明の範囲をはずれるものだった。
〔比較例3〜6〕
実施例1の綿を含む廃棄材料を、それぞれ表1の条件で、回収綿を得ようとした。得られた回収綿の回収率および物性は表1に記す。回収綿は得られたものの、重合度DPはいずれの例も本発明の範囲をはずれており、さらに、平均粒径又は質量減量率のいずれかが本発明の範囲をはずれるものだった。
[Comparative Examples 1 and 2]
Using the waste material containing the cotton of Example 1 and sulfuric acid, the recovered cotton was obtained under the conditions shown in Table 1. Table 1 shows the recovery rate and physical properties of the recovered cotton. Although recovered cotton was obtained, the mass loss rate after high-temperature treatment and the content of sulfur element were high, and were outside the scope of the present invention.
[Comparative Examples 3 to 6]
The waste material containing the cotton of Example 1 was tried to obtain recovered cotton under the conditions shown in Table 1. Table 1 shows the recovery rate and physical properties of the recovered cotton. Although recovered cotton was obtained, the degree of polymerization DP was out of the scope of the present invention in any case, and either the average particle size or the weight loss rate was out of the scope of the present invention.
〔実施例11〕
脂肪族ポリエステル90gと実施例1で得られた回収綿30gを二軸押し出し機にて混練し、180℃にて押し出した。得られた組成物でダンベルを成形し、得られた成形品について評価を行った。評価の結果、3点曲げ剛性は6630MPa、破断強度は58MPa、繊維の分散状態は均一だった。
〔比較例7〕
回収綿を用いない以外は、実施例11と同様に成形及び評価を行った。評価の結果、3点曲げ剛性は870MPa、破断強度は49MPaであり、実施例11と比べて3点曲げ剛性、破断強度共に劣る結果となった。
Example 11
90 g of aliphatic polyester and 30 g of the recovered cotton obtained in Example 1 were kneaded with a biaxial extruder and extruded at 180 ° C. Dumbbells were molded from the obtained composition, and the obtained molded products were evaluated. As a result of the evaluation, the three-point bending rigidity was 6630 MPa, the breaking strength was 58 MPa, and the fiber dispersion state was uniform.
(Comparative Example 7)
Molding and evaluation were performed in the same manner as in Example 11 except that the recovered cotton was not used. As a result of the evaluation, the three-point bending rigidity was 870 MPa, and the breaking strength was 49 MPa, and both the three-point bending rigidity and breaking strength were inferior to those of Example 11.
〔比較例8〕
比較例1で得られた回収綿を用いた以外は、実施例11と同様に成形及び評価を行った。評価の結果、3点曲げ剛性は4040MPa、破断強度は47MPa、繊維の分散状態は均一であり、実施例11と比べて3点曲げ剛性、破断強度共に劣る結果となった。
〔比較例9〕
比較例4で得られた回収綿を用いた以外は、実施例11と同様に成形及び評価を行った。。評価の結果、3点曲げ剛性は5920MPa、破断強度は55MPaと実施例11と比べて3点曲げ剛性
、破断強度は共に大差がなかったものの、繊維の分散状態が不均一だった。
(Comparative Example 8)
Molding and evaluation were performed in the same manner as in Example 11 except that the recovered cotton obtained in Comparative Example 1 was used. As a result of the evaluation, the three-point bending stiffness was 4040 MPa, the breaking strength was 47 MPa, the fiber dispersion state was uniform, and the three-point bending stiffness and breaking strength were inferior to those of Example 11.
(Comparative Example 9)
Molding and evaluation were performed in the same manner as in Example 11 except that the recovered cotton obtained in Comparative Example 4 was used. . As a result of the evaluation, the three-point bending stiffness was 5920 MPa and the breaking strength was 55 MPa, which was not significantly different from the three-point bending stiffness and breaking strength, but the fiber dispersion state was not uniform.
〔実施例12〕
二軸の攪拌翼を有する反応機に回収綿1.0gを、ピリジン10ml及び無水酢酸5mlとともに反応容器に入れて、25℃で約48時間、アセチル化反応を行った。これにメタノールを200ml加えた後、沈殿物をろ過し、このようにして得られた生成物をメタノール100mlで洗浄し、乾燥させることによりアセチルセルロース1.6g(置換度2.9)を得た。
Example 12
In a reactor having a biaxial stirring blade, 1.0 g of recovered cotton was placed in a reaction vessel together with 10 ml of pyridine and 5 ml of acetic anhydride, and acetylation reaction was carried out at 25 ° C. for about 48 hours. 200 ml of methanol was added thereto, the precipitate was filtered, and the product thus obtained was washed with 100 ml of methanol and dried to obtain 1.6 g of acetylcellulose (substitution degree 2.9).
本発明の回収綿は、コンポジット、発酵原料、誘導体原料に有効に利用することができる。また効果的な綿のリサイクルにより高度の利用が可能となれば持続的な社会の発展に必要な、省資源、省エネルギー、地球温暖化防止技術と多いに寄与するものである。 The recovered cotton of the present invention can be effectively used for composites, fermentation raw materials, and derivative raw materials. In addition, if advanced utilization becomes possible by effective cotton recycling, it will contribute to many resources and energy saving and global warming prevention technologies necessary for sustainable social development.
Claims (3)
(a) 綿を含む繊維製品廃棄材料を１〜１００ｍｍ角に裁断する工程
(b) ０．０５〜１ｗｔ％のＨＣｌ水溶液に(a)で得られた裁断物を０．１〜４０ｗ
ｔ％で投入する工程
(c) １００〜１５０℃で１０分〜４時間処理する工程
(d) ８０℃以下まで冷却後、溶液中のｐＨを６．５〜８．２になるまで中和し、１〜２０ｗｔ％のスラリー濃度になるように水を投入する工程
(e) 二軸の攪拌翼を有する反応機で、５０〜５００ｒｐｍで１０分〜５時間攪拌し、圧搾する工程
(f) (e)で回収した綿繊維を１０５〜１２０℃で１０分〜５時間で乾燥する工程 Following (a) ~ a method for separating and recovering cotton claim 1, wherein the textile waste material comprising cotton, characterized in that it comprises the steps of (f).
(a) The process of cutting the textile waste material containing cotton into 1 to 100 mm square
(b) 0.1-40 w of the cut product obtained in (a) in 0.05-1 wt% HCl aqueous solution
Process to be input at t%
(c) The process of processing at 100-150 degreeC for 10 minutes-4 hours
(d) A step of cooling to 80 ° C. or lower, neutralizing the pH of the solution to 6.5 to 8.2, and adding water so that the slurry concentration becomes 1 to 20 wt%.
(e) Step of stirring and squeezing at 50 to 500 rpm for 10 minutes to 5 hours in a reactor having biaxial stirring blades
(f) A step of drying the cotton fibers collected in (e) at 105 to 120 ° C. for 10 minutes to 5 hours.
を特徴とする請求項２記載の綿を含む繊維製品廃棄材料から綿を分離・回収する方法
(g) (f)で得られた回収綿を粉砕する工程 The method for separating and recovering cotton from textile waste material containing cotton, further comprising (g), and separating and recovering cotton from textile waste material containing cotton according to claim 2
(g) A step of pulverizing the recovered cotton obtained in (f)
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