US20210381166A1 - Processing cellulose-containing materials for paper or packaging materials - Google Patents
Processing cellulose-containing materials for paper or packaging materials Download PDFInfo
- Publication number
- US20210381166A1 US20210381166A1 US17/342,160 US202117342160A US2021381166A1 US 20210381166 A1 US20210381166 A1 US 20210381166A1 US 202117342160 A US202117342160 A US 202117342160A US 2021381166 A1 US2021381166 A1 US 2021381166A1
- Authority
- US
- United States
- Prior art keywords
- pulp
- cellulose
- textile
- wood
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920002678 cellulose Polymers 0.000 title claims description 146
- 239000001913 cellulose Substances 0.000 title claims description 144
- 239000000463 material Substances 0.000 title claims description 81
- 238000012545 processing Methods 0.000 title claims description 36
- 239000005022 packaging material Substances 0.000 title description 7
- 238000000034 method Methods 0.000 claims abstract description 96
- 239000004753 textile Substances 0.000 claims abstract description 91
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 32
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 235000010980 cellulose Nutrition 0.000 claims description 145
- 239000000835 fiber Substances 0.000 claims description 131
- 239000000123 paper Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000002023 wood Substances 0.000 claims description 18
- 239000011111 cardboard Substances 0.000 claims description 15
- 229920003043 Cellulose fiber Polymers 0.000 claims description 14
- 229920005610 lignin Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims description 5
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- 229920003086 cellulose ether Polymers 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000004537 pulping Methods 0.000 description 82
- 238000011282 treatment Methods 0.000 description 52
- 229920000742 Cotton Polymers 0.000 description 50
- 230000008569 process Effects 0.000 description 42
- 239000000243 solution Substances 0.000 description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 241000219146 Gossypium Species 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 31
- 239000007787 solid Substances 0.000 description 28
- 239000003153 chemical reaction reagent Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 25
- 238000004090 dissolution Methods 0.000 description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 18
- 239000004744 fabric Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 16
- 230000001590 oxidative effect Effects 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 13
- 239000012736 aqueous medium Substances 0.000 description 12
- 229920000297 Rayon Polymers 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
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- 239000003638 chemical reducing agent Substances 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 10
- 238000002203 pretreatment Methods 0.000 description 10
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- 238000000926 separation method Methods 0.000 description 10
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- -1 apparel Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 9
- 230000002255 enzymatic effect Effects 0.000 description 9
- 239000002608 ionic liquid Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 238000010936 aqueous wash Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- LGECYHKACRVEKY-UHFFFAOYSA-L copper;azane;dihydroxide Chemical compound N.N.N.N.[OH-].[OH-].[Cu+2] LGECYHKACRVEKY-UHFFFAOYSA-L 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 3
- 239000005750 Copper hydroxide Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 240000000047 Gossypium barbadense Species 0.000 description 3
- 235000009429 Gossypium barbadense Nutrition 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010817 post-consumer waste Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000001433 sodium tartrate Substances 0.000 description 3
- 229960002167 sodium tartrate Drugs 0.000 description 3
- 235000011004 sodium tartrates Nutrition 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 238000002955 isolation Methods 0.000 description 2
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Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/14—Secondary fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/08—Mechanical or thermomechanical pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets
Definitions
- the present disclosure relates to methods and systems for processing cellulose-containing materials such as textiles, including textile garments (used and un-used) and scraps, biomass, wood pulp, and the like and for isolating cellulose molecules for use in a variety of downstream applications.
- the present disclosure relates to methods and systems for treatment of cellulose-containing materials to isolate cellulose molecules and to produce regenerated polymers, fibers, fabrics, the like, or combinations or multiples thereof from the isolated cellulose molecules. Recycling and regeneration of textiles is described in detail and provides significant social, environmental and economic benefits.
- Cotton clothing is estimated to represent about 35% of the total apparel market.
- Cotton fibers are composed of cellulose, a naturally occurring polymer found in all plants, wood, and natural fibers. Cotton fibers are harvested from cotton plants and consist of long, interwoven chains of cellulose polymers. These fibers are spun into thread or yarn, dyed, and ultimately woven, knit, and assembled into textiles. Natural fibers, including cotton, have a generally high and variable raw material cost due, in part, to natural disasters and climate unpredictability, regional socio-economic and political instability, human rights issues, and resource requirements.
- Cotton has been recycled to provide raw material for paper pulping plants. Re-processing methods that convert used cotton into rags, mattress ticking, seat stuffing, insulating materials, and the like are also available, but these processing methods have been adopted in limited applications because the value of the converted material is relatively low.
- rayon fibers are manufactured from wood pulp using the viscose process.
- purified cellulose is solubilized and then converted or regenerated into cellulose fiber.
- This process requires steeping, pressing, shredding, aging, xanthation, dissolving, ripening, filtering, degasing, spinning, drawing and washing.
- This process is time sensitive, requires multiple chemical treatments, produces lignin and other waste from unusable wood material and is, at best, a semi-continuous manufacturing process.
- the present disclosure is directed to providing systems and methods for processing cellulose-containing feedstocks, such as recycled fabric, fabric scraps and other cellulose containing materials, many of which would otherwise be wasted or used to produce low value products, to isolate their constituent cellulosic polymeric structures.
- the polymeric cellulosic structures are then used in industrial processes such as fabric production.
- Implementation of the disclosed processing schemes with a variety of garment/fabric feedstock materials may produce regenerated fibers and textile products having improved, customizable, or both properties using processes having low environmental impacts.
- Methods and systems of the present disclosure relate to processing of cellulose-containing materials including, for example, postconsumer cellulosic waste, cellulose-containing textiles and garments (e.g., recycled or used or waste textiles and garments), virgin cotton, wood pulp, biomass, and the like, to produce isolated cellulose polymers for use in downstream processing applications.
- cellulose-containing materials used as raw feed material for processing comprise discarded garments, scrap fabric materials, or both, and processing produces isolated cellulose polymers that can be further processed and extruded to provide regenerated fibers having improved, customizable, or both properties for use in textile industries or for other purposes.
- a multi-stage process is described, incorporating one or more pretreatment stages providing removal of contaminants and preparation of cellulosic materials, followed by pulping, molecular separation of cellulose polymers, or both.
- the pretreatment and pulping processes may be carried out in a continuous, semi-continuous or batch system.
- the pretreatment and pulping processes may be carried out in one or more closed reaction vessel(s), and processing reagents may be recovered and re-used or processed for other uses.
- pretreatment processing stages are described and may be used alone or in combination to remove non-cellulosic constituents of the feed and prepare cellulosic components for pulping and dissolution.
- Pretreatment is followed by at least one cellulose pulping or dissolution stage that promotes the molecular separation and isolation of cellulose polymers, such as by disrupting intermolecular hydrogen bonds.
- cellulosic polymers isolated during the pulping stage, the dissolution stage, or both are substantially thermoplastic and are moldable when energy (e.g., heat below the char point) is introduced to the system.
- Isolated cellulose polymers produced using the processes described herein may be used in a variety of downstream applications, as described in more detail below and, in some embodiments, may be extruded to form regenerated cellulosic fibers.
- isolated cellulose polymers may be re-generated to provide longer chain polymers and fibers (or polymers and fibers having other desirable characteristics different from the characteristics of the cellulose-containing feedstock) that are useful in various industrial processes, including textile production.
- processing steps having generally low environmental impacts are preferred.
- methods and systems of the present disclosure provide a closed-loop garment recycling process that transforms reclaimed garments and textiles into high-quality, bio-based fiber for use in creating new textiles, apparel, and other fiber-based products.
- Used and waste garment collection, sorting, transport and processing may all be involved as part of a closed loop process.
- Retail enterprises and others may serve as collection stations and may offer incentives, rewards, or the like for donations. Further garment processing may take place at the donation site or at one or more remote sites. Cotton, cotton-like regenerated fabrics, rayon and other fibers may be produced using the reclaimed garments and textiles.
- FIG. 1 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to liquefied cellulose suitable for use in a variety of downstream applications.
- FIG. 2 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber and incorporating one or more of a variety of pretreatments.
- FIG. 3 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating a high temperature aqueous or supercritical carbon dioxide pretreatment step and incorporating optional additional treatment steps.
- FIG. 4 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating a combination of pretreatment steps.
- FIG. 5 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating another combination of pretreatment steps.
- FIG. 6 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating another combination of pretreatment steps.
- FIG. 7 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating yet another combination of pretreatment steps.
- FIG. 8 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for processing blended textile input to produce liquefied cellulosic and polymeric output.
- FIG. 9A shows a magnified image of a regenerated cellulosic fiber produced as described herein
- FIG. 9B shows a magnified image of a premium long-staple cotton fiber as tested in Harzallah, Benzina & Drean, 2009
- FIG. 9C shows an enlarged, cross-sectional view of a regenerated cellulosic fiber produced as described herein.
- FIG. 10 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for producing paper or packaging materials from a combination pulp including a textile pulp and a wood pulp.
- systems and methods disclosed herein process cellulose-containing materials to produce isolated cellulosic polymers suitable for use in downstream processing and a variety of downstream applications and production pathways.
- Cellulose-containing materials that are useful as raw materials for this process include a wide range of materials, such as cellulose-containing postconsumer waste, biomass materials and pulp (e.g., wood pulp), cotton and cotton-containing materials, and the like, including unworn or worn and discarded cotton and cotton-containing apparel, as well as scrap cotton fiber and fabric.
- the cellulose-containing feedstock undergoes at least one pretreatment stage (and optionally multiple pretreatment stages) and at least one pulping or dissolution stage to produce isolated cellulose molecules suitable for use in various different application pathways.
- the raw cellulose-containing feed material may be substantially homogeneous (e.g., pre- or post-consumer waste, scrap textile fiber and fabric, cotton-containing fabrics, biomass or pulped wood or biomass, etc.), or it may be at least somewhat heterogeneous (e.g., cellulose-containing materials from mixed sources and of mixed types).
- used clothing collection and sorting may be accomplished via clothing retailers, manufacturers, recyclers, and various other organizations, providing access to large volumes of used, cellulose-containing garments and scrap materials that would otherwise be discarded.
- optional sorting and removal of non-cellulosic components may be carried out prior to pretreatment of the cellulose-containing feedstock.
- reclaimed garments and textiles When reclaimed garments and textiles are used as cellulose-containing feed material, initial sorting of reclaimed garments and textiles according to fiber content may be advantageous prior to feedstock pretreatment and dissolving.
- reclaimed material e.g., garments and textiles
- cellulosic content e.g., reclaimed materials may be separated into groups having different cellulosic contents, such as >90% or >80% or >70% or >50%, or other cellulosic contents, and less than 50% cellulosic content.
- Reclaimed fabric material having other fiber contents and compositions may also be sorted and separated, and reclaimed material may also be sorted by composition, such as separating cotton-wool blends, cotton-polyester blends, cotton-elastane blends, cotton-spandex blends, and the like. Separation of non-cellulosic-containing materials such as buttons, zippers, and the like may take place at the time of or following sorting and process pretreatment. Likewise, mechanical sizing or comminution, such as shredding, pulling, grinding, cutting, tearing, and the like may take place prior to or following sorting and process pretreatment.
- Cellulosic feedstocks such as reclaimed garments and textiles typically incorporate a variety of dyes, chemical finishes, or both, and may be contaminated with other materials, such as dirt, grease, and the like.
- Other types of cellulosic feedstocks such as biomass, postconsumer waste, and the like, also contain contaminants that are desirably removed prior to a pulping stage.
- Raw cellulose-containing feedstock (optionally treated to remove non-cellulose-containing materials, and optionally sized) is typically processed in one or more pre-treatment stage(s) to remove dyes, finishes, contaminants (oils, grease, etc.) and the like from the feedstock.
- Cellulosic feedstocks including textile materials may optionally be mechanically treated to provide smaller sized, or more uniformly sized, feedstock.
- the fabric feedstock may be sized if desired, such as by shredding, to provide a sized feedstock having a fragmented, high surface area for fiber pulping.
- Feedstock sizing is typically accomplished using mechanical cutting, shredding, or other mechanical size reduction techniques. Processing to remove non-cellulosic components, such as buttons, zippers, fasteners, and the like may take place, if desired, prior to pretreatment, following pretreatment, or both.
- pre-treatment stages are described below, and various combinations of pretreatment stages may provide benefit, depending on the nature of the cellulosic feedstock. Depending on the properties of the raw textile feedstock, one or more of the pretreatments may be used, alone or in combination with other pretreatments. Several (optional) pre-treatment stages are described below, and several advantageous pre-treatment combinations are also described. It will be appreciated that additional pre-treatments may be used in combination with the pre-treatments described, and that various specific combinations other than those specifically illustrated and described may be used.
- FIG. 1 illustrates an overall process flow diagram for treating cellulose-containing materials to produce isolated cellulose polymers, identified in FIG. 1 as “Liquefied Cellulose,” suitable for use in a variety of downstream applications, such as fiber production (e.g., textiles, technical fibers and geo-textiles), production of other extrusion manufacturing methods, constructional manufacturing methods (e.g., 3D printing media, membranes, injection molding media), or both, use as a chemical feedstock for production of biofuels, lubricants and other chemical manufacturing, and for use as food additives, in films, coating, fillers, membranes, packaging, construction materials, non-woven materials, and the like.
- fiber production e.g., textiles, technical fibers and geo-textiles
- constructional manufacturing methods e.g., 3D printing media, membranes, injection molding media
- food additives e.g., in films, coating, fillers, membranes, packaging, construction materials, non-woven materials, and the like.
- FIGS. 1 and 2 illustrates an overall process flow diagram for treating cellulose-containing materials to produce liquefied cellulose suitable for fiber extrusion and including additional processing stages for production of regenerated cellulosic fiber.
- the cellulose-containing materials may undergo similar pretreatment and the pulping stage, the dissolution stage, or both, as illustrated in FIGS. 1 and 2 , while the isolated cellulose product may be used for different applications, as shown.
- cellulose-containing feed materials may undergo optional feedstock preparation stages, such as feedstock sorting, removal of non-cellulosic components, or both.
- the cellulose-containing feedstock then undergoes at least one pretreatment stage, followed by pulping or, dissolution of, or both, the pretreated cellulose-containing feedstock and filtration to produce isolated cellulose polymers.
- pretreatment stages are described below and are illustrated in the accompanying diagrams.
- one or more than one of the pretreatment stages may be used alone or in combination with other pretreatment stages. Specific combinations of pretreatments that may be useful in particular applications are described in greater detail below with reference to FIGS. 3-7 .
- Each of the pretreatment stages is described in more detail below.
- methods disclosed herein provide pretreatment of cellulose-containing feed materials using a high temperature aqueous washing process.
- This pretreatment stage is particularly useful for pretreatment of cellulose-containing feed materials comprising recycled garments and may facilitate removal of contaminants such as soils, deodorants, lanolin, silicone and cationic softeners from the feedstock, as well as stripping various fabric treatments, such as optical brighteners, moisture wicking enhancers, and the like, from the feed material.
- Aqueous media maintained at a temperature above 100° C., optionally above the boiling point of the aqueous media, generally above 120° C., often between 120° C. and 170° C., sometimes between 130° C. and 150° C., and up to 200° C., may be used.
- the high temperature aqueous washing pretreatment stage is conducted in a closed vessel batch system with circulation or agitation or mixing of the hot aqueous media.
- Pressure conditions in a closed vessel system may range from about 100 kPa to about 2000 kPa, depending on the temperature of the aqueous media, with higher pressure conditions accompanying higher temperature media.
- Aqueous media used in a high temperature pretreatment stage may comprise water alone, or it may comprise an aqueous solution having one or more additives.
- the aqueous media may comprise water enriched with ozone.
- the aqueous media may comprise water enriched with oxidative agents such as hydrogen peroxide or sodium perborate.
- surfactants e.g., Sodium stearate, Fatty Alcohols, 4-(5-Dodecyl) benzenesulfonate, Alcohol ethoxylates and the like
- various hydroxide compositions e.g., Ca, Mg, Na, K, and Li hydroxides
- the high temperature aqueous washing stage incorporates an aqueous solution comprising NaOH at a concentration of from about 1% to about 15%, at a pHin excess of about 11, and in some embodiments in excess of about 12. Residence times are sufficient to substantially remove impurities from the cellulose-containing feedstock.
- the aqueous wash solution may be evacuated following a suitable residence time.
- multiple aqueous washing stages may be implemented, using the same or different aqueous solutions, all at high temperature and pressure conditions.
- Optional rinsing of the solids with an aqueous solution may be implemented following evacuation of the wash solution. Rinsing may take place at ambient temperatures and pressures, with optional agitation and mixing, and the rinse solution is removed following a suitable residence time.
- Cellulose-containing treated solids may undergo one or more additional pretreatment stage(s) or may be further processed in a pulping stage, a dissolution stage, or both.
- a water-less pretreatment, “non-toxic” pretreatment, or both may be used to remove contaminants such as dyes, finishes, surface impurities and other contaminants from cellulose-containing feed materials, and particularly from feed materials comprising recycled garments or textiles.
- cellulose-containing feed material may be introduced to a closed and pressurized chamber, where the feed material contacts supercritical carbon dioxide, alone or in combination with additional reagent(s).
- the supercritical CO2 may be enriched with ozone.
- the supercritical CO2 may enriched with oxidative agents such as hydrogen peroxide or sodium perborate.
- surfactants e.g., Sodium stearate, Fatty Alcohols 4-(5-Dodecyl) benzenesulfonate, Alcohol ethoxylates and the like
- surfactants may be mixed and circulated with the supercritical CO2 in a pretreatment stage.
- supercritical carbon dioxide containing dissolved contaminants is withdrawn to a separator, where the carbon dioxide may be decompressed and returned to a gaseous state, while the contaminants may be collected and removed.
- the gaseous carbon dioxide may be recycled in a closed loop process and re-used for additional pretreatment cycles.
- Cellulose-containing treated solids may undergo one or more additional pretreatment stage(s) or may be further processed in a pulping stage, a dissolution stage, or both.
- cellulose-containing feedstock, cellulose-containing treated solids, or both are treated, prior to pulping or dissolution, with a high temperature (>320° C.), high pressure (>2.5 Mps) aqueous treatment, in a closed and substantially rigid reaction vessel.
- This pretreatment stage promotes breakdown of the crystalline structure of cellulose and facilitates modification of cellulosic constituents to an amorphous, non- or less-crystalline structure that is more amenable to pulping, dissolution, or both.
- a pretreatment stage involves exposing the cellulose-containing feed material (or cellulose-containing treated solids, or both) to a “bleaching” agent, such as an oxidative or reducing agent, typically in an aqueous solution, at an oxidative/reducing agent concentration and for a residence time sufficient to remove materials such as dyes, finishes, and other contaminants from the cellulosic feedstock.
- a “bleaching” agent such as an oxidative or reducing agent
- Suitable oxidative agents, reducing agents, or both include, for example, peroxide compositions (e.g., H 2 0 2 , Na 2 O 2 ) and perborate (e.g., NaBO 3 ) compositions.
- Additional oxidative agents, reducing agents, or both, that may be used in pretreatment stages as described herein include one or more of the following compositions: per carbonate compositions; sodium carbonate; per acetic acid compositions; potassium permanganate; persulfate compositions; ozone; sodium chloride; calcium oxychloride, sodium hypochlorite; calcium hypochlorite; lithium hypochlorite; cloramine; isocynual trichloride; Sulphur dioxide; sodium hydrosulfite; sulphoxylates; acidic sodium sulphite; sodium bosulphite; sodium meta bisulphite; TAED (tetra-acetyl-ethylene-diamine); and sodium hydrosulfite.
- per carbonate compositions sodium carbonate
- per acetic acid compositions potassium permanganate
- persulfate compositions ozone
- sodium chloride calcium oxychloride, sodium hypochlorite; calcium hypochlorite; lithium hypoch
- bleaching agent treatment may involve treatment in an aqueous solution of calcium hypochloride (bleach powder) or sodium hypochlorite (NaOCl) in combination with sodium carbonate (soda ash) at a pH in excess of 8 and, in some embodiments, at a pH in excess of 9. Agitation or mixing of the materials in the bleaching agent pretreatment stage may be provided, and treatment with an oxidative, a reducing agent, or both, may take place in a closed reaction vessel.
- an oxidative, a reducing agent, or both may take place in a closed reaction vessel.
- the bleaching agent solution may be evacuated following a suitable residence time and optional rinsing of the solids with an aqueous solution may be implemented. Aqueous rinsing may take place at ambient temperatures, with the rinse solution removed following a suitable residence time.
- the bleaching agent may be neutralized, following this treatment, by introduction of a weak acid such as hydrogen peroxide.
- a weak acid such as hydrogen peroxide.
- multiple bleaching agent treatment cycles may be implemented using different oxidative or reducing reagents to treat the solids at different concentrations, pH conditions, temperature, residence times, the like, or combinations or multiples thereof, as appropriate. Recycling and regeneration of the oxidative or reducing agent(s) may be incorporated in the process, as is known in the art. Introduction of other weak acids may be effective to reduce the pH of the treated, cellulose-containing solids, if desired, following optional rinsing steps.
- methods disclosed herein provide pretreatment of cellulose-containing feed materials (or cellulose-containing treated solids, or both) by exposure to aqueous media containing one or more organic solvents.
- Suitable organic solvents may be selected from the group consisting of: acetic acid; acetone; acetonitrile; benzene; 1-butanol; 2-butanol; 2-butanone; t-butyl alcohol; carbon tetrachloride; chlorobenzene; chloroform; cyclohexane, 1,2-di chloroethane; diethylene glycol; di ethyl ether; diglyme (diethylene glycol dimethyl ether); 1,2-dimethoxy-ethane (glyme, DME); dimethyl formamide (DMF); dimethyl sulfoxide (DMSO); 1,4-dioxane; ethanol, ethyl acetate; ethylene glycol; glycerin; heptane; hexa
- methods disclosed herein may optionally employ enzymatic treatment to shorten cellulose molecules, increase cellulose solubility, reduce reaction times, or both, in subsequent treatment stages.
- Suitable enzymes may include endogluconases (e.g., Cel 5A, Cel 7B, Cel 12A, Cel 45, Cel 61A); Cellobiohydrolases (e.g., Cel 6A, Cel 7A); LPMO/GH6 l; cellulases; and the like.
- temperatures of from about 30° to 90° C., pH between about 4 to about 9 and dwell times of from about 20 min to 48 hours may be suitable for enzymatic treatment.
- Enzymatic treatment(s) involving xylanases, alkaline pectinases, lipases, esterases, the like, or combinations or multiples thereof may also be used for feedstock pretreatment prior to pulping.
- feedstock may be treated using enzymatic cultures containing biological organisms (fungi, bacteria, etc.) that secrete cellulolytic enzymes (e.g., cellulases).
- Enzyme cultures such as Trichoderma Reesei, Trichoderma viride, Penicillium janthinellum, Halorhabdusutahensis, A Niger, Humicola , and mixtures of such enzyme-producing cultures, are suitable.
- Mechanical treatments such as pulverization, emulsification treatment(s), or both, may be implemented following enzymatic treatment.
- a swelling agent such as an ionic liquid
- treatment with a swelling agent may be preceded by or implemented in combination with one or more other pretreatment stage(s).
- Ionic liquids may comprise hydroxides, such as Ca, Mg, Na, K, Li hydroxides, the like, or combinations or multiples thereof.
- Swelling agents suitable for use as reagents in a pretreatment stage may alternatively or additionally comprise one or more of the following reagents: [AMIM]Cl 1-Allyl-3-methylimidazolium chloride; [BzPy]Cl Benzylpyridinium chloride; [BMIM]Ace 1-Butyl-3-methylimidazolium acesulphamate; [BMIM]DBP 1-Butyl-3-methylimidazolium dibutylphosphate; [BMIM]Cl 1-Butyl-3-methylimidazolium chloride; [BMIM]PF6 1-Butyl-3-methylimidazolium hexafluorophosphate; [BMIM]BF4 1-Butyl-3-methylimidazolium tetrafluoroborate; [BMPy]Cl 1-Butyl-3-methylpyridinium chloride; [DBNH]AcO 1,8-Diazabicyclo[5.4.0]undec-7-enium acetate; [DB
- cellulose-containing feed materials may be treated with an ionic solution such as an aqueous solution comprising Ca, Mg, Na, K, Li hydroxides, the like, or combinations or multiples thereof, followed by exposure to a sodium hydrosulfite (Na 2 S 2 0 4 ) reducing agent, a bleaching agent such as peroxide, perborate, persulfate, and sodium or calcium hypochlorite, or both.
- an ionic solution such as an aqueous solution comprising Ca, Mg, Na, K, Li hydroxides, the like, or combinations or multiples thereof
- a sodium hydrosulfite (Na 2 S 2 0 4 ) reducing agent such as peroxide, perborate, persulfate, and sodium or calcium hypochlorite, or both.
- a bleaching agent such as peroxide, perborate, persulfate, and sodium or calcium hypochlorite, or both.
- Bromium (Br) may be used as a
- Treatment with swelling agents such as ionic liquids may be achieved using high temperature or cooler aqueous wash media.
- treatment with a swelling agent e.g., an ionic liquid
- a swelling agent e.g., an ionic liquid
- the treatment may be carried out at an acidic pH, typically at a pH less than 6, and in some embodiments at a pH less than 5.
- the proportion of cellulose-containing feed materials (or cellulose-containing treated solids, or both) in the ionic solution is from about 2% to about 40%; in some embodiments, the proportion of cellulose-containing feed materials (or cellulose-containing treated solids, or both) in the ionic solution is from about 5% to about 25%.
- Pretreatment of cellulose-containing feedstock material may implement any of these pretreatment processes, singly or in combination with one or more other pretreatment processes.
- carrying out elevated temperature aqueous pretreatment in a closed vessel is preferred, alone or in combination with other pretreatment stages, prior to pulping and dissolution of the cellulose polymers.
- carrying out elevated temperature aqueous pretreatment with the use of ozone enrichment, oxidative agents, surfactants, the like, or combinations or multiples thereof is preferred, alone or in combination with other pretreatment stages, prior to pulping.
- pretreatment involves elevated temperature aqueous pretreatment, followed by ionic pretreatment, followed by enzymatic pretreatment.
- one or more of the pretreatment stages, or all pretreatment stages are carried out a pH of at least about 9.
- one or more of the pretreatment stages, of all of the pretreatment stages are carried out at a pH of at least about 10.
- Pretreatment preferably takes place in a closed vessel and, in batch treatment schemes, one or more pretreatment reagents may be introduced to and withdrawn from a closed vessel during various pretreatment stages, with or without intermediate rinsing or washing stages.
- the vessel may be provided in the form of a rotating cylinder with a pressurized hull (housing) capable of withstanding pressures in the range of from 1000-5000 kPa, having inlet and outlet ports, pH and rpm control features, and having liquid agitation or circulation features.
- the inner reaction vessel surfaces may comprise anticorrosive metal(s) capable of withstanding concentrated acidic and alkali solutions. In some processes, both pretreatment and pulping may take place in the same vessel.
- FIGS. 3-7 Specific pretreatment combinations are described below with reference to the schematic flow diagrams shown in FIGS. 3-7 .
- Each of these flow diagrams describes different feedstock pretreatment combinations, followed by molecular isolation and separation of cellulose polymers in a pulping or dissolution stage.
- Cellulose polymers may be separated from the pulping solution, such as by filtration, and regenerated cellulosic fibers may be extruded, such as in connection with a precipitation bath (e.g., an acid bath). Extruded fibers may be designed and parameters changed, depending on the type, character and physical attributes of the cellulosic fibers desired. Drying and winding produces regenerated cellulosic fibers.
- FIG. 3 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with ozone enrichment, oxidative agent(s), surfactant(s), the like, or combinations or multiples thereof.
- the cellulosic solids may optionally be treated with swelling agents (as described above), with organic solvents (again, as described above), or both.
- These treatment stages may be done at elevated temperatures or in cooler aqueous media.
- FIG. 4 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with oxidative agent(s), surfactant(s), or both.
- the cellulosic solids may optionally undergo enzymatic treatment as described above.
- the cellulosic solids may subsequently be exposed to swelling agents such as ionic liquids (e.g., NaOH) prior to a pulping or dissolution stage.
- FIG. 5 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with oxidative agent(s), surfactant(s), or both.
- the cellulosic solids may optionally be exposed to swelling agents such as ionic liquids (e.g., NaOH), followed by enzymatic treatment as described above prior to a pulping or dissolution stage.
- swelling agents such as ionic liquids (e.g., NaOH)
- FIG. 6 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with optional ozone enrichment, oxidative agent(s), surfactant(s), the like, or combinations or multiples thereof.
- the cellulosic solids may optionally be exposed to swelling agents such as ionic liquids (e.g., NaOH), followed by exposure to bleaching agents, reducing agents, an enzyme treatment, the like, or combinations or multiples thereof, all as described above, prior to a pulping or dissolution stage.
- swelling agents such as ionic liquids (e.g., NaOH)
- bleaching agents e.g., reducing agents, an enzyme treatment, the like, or combinations or multiples thereof, all as described above, prior to a pulping or dissolution stage.
- FIG. 7 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with optional ozone enrichment, oxidative agent(s), surfactant(s), the like, or combinations or multiples thereof.
- the cellulosic solids may optionally undergo a high-temperature, high-pressure aqueous treatment stage, as described above, to promote destruction of the cellulosic crystalline structure and favor conversion of cellulosic polymers to an amorphous phase.
- the cellulosic solids may be exposed to enzyme treatment, as described above, prior to a pulping or dissolution stage.
- Treated cellulose-containing solids are subjected to a pulping or dissolving stage, in which the cellulose-containing solids are treated in a pulping reagent to promote molecular separation of cellulose polymers and destruction of intermolecular hydrogen bonds and other non-covalent bonds, converting cellulose-containing solids to their constituent cellulose polymers.
- the number of intermolecular hydrogen bonds present in the cellulose polymers is reduced by at least 20% in the fiber pulping stage; in some embodiments the number of intermolecular hydrogen bonds present in the cellulose polymers is reduced by at least 50% in the fiber pulping stage; in yet other embodiments, the number of intermolecular hydrogen bonds present in the cellulose polymers is reduced by at least 70% in the fiber pulping stage.
- the viscosity of pulped cellulose, following the pulping treatment is generally from about from 0.2 to as high as 900 cP, often from about 0.5 to about 50 cP.
- pulping techniques and pulping chemistries are available, and one or more of the pretreatment stages described above may be used with a variety of known pulping reagents, including those described in PCT Int'l Patent Publication WO 2013/124265 A1, the disclosure of which is incorporated herein by reference in its entirety.
- copper-containing reagents are preferred for use as pulping reagents.
- Schwiezer's Reagent the chemical complex tetraaminecopper (II) hydroxide —[Cu(NH 3 ) 4 (H 2 0) 2 ]) or tetraamminediaquacopper dihydroxide, [Cu(NH 3 ) 4 (H 2 0) 2 ](0 H) 2 is a preferred pulping agent to isolate and promote molecular separation of cellulose polymers.
- Schweizer's reagent may be prepared by precipitating copper(II) hydroxide from an aqueous solution of copper sulfate using sodium hydroxide or ammonia, then dissolving the precipitate in a solution of ammonia.
- a combination of caustic soda, ammonium and cupramonium sulfate may be formulated to provide Schwiezer's Reagent.
- Solutions comprising copper(II) hydroxide and ammonia may be introduced and used in the pulping stage to form Schweizer's Reagent according to the following reaction: Cu(OH) 2 +4NH 3 +2H 2 O ⁇ [Cu(NH 3 ) 4 (H 2 O) 2 ] 2+ +20H.
- the copper hydroxide reagent may be manufactured from recycled copper recovered, for example, from electronics and computer component waste materials. Copper hydroxide is readily made from metallic copper by the electrolysis of water using copper anodes.
- Ammonia may be manufactured by an innovative use of the Haber-Bosch process (3H 2 +N 2 ⁇ 2NH 3 ) capturing hydrogen from organic wastes and combining it with atmospheric nitrogen.
- This method may produce ammonia at low cost and eliminate greenhouse gas emissions from organic waste feedstock.
- all or substantially all of the materials used in the fiber pulping process described herein may be sourced as waste products, resulting in minimal or no use of nonrenewable resources.
- FeTNa iron tartrate complex solvents
- FeTNa solutions may be prepared according to the procedure published by Seger et al. (B. Seger, et al., Carbohydrate Polymers 31 (1996) 105.) FeTNa solutions are prepared and stored while protecting them from light.
- the FeTNa complex may be prepared, for example, by dissolving sodium tartrate dehydrate (Alfa Assar, Cat. #16187) in deionized water, stirring and optionally heating.
- iron nitrate nonahydrate Alfa Aesar, Cat. #122266
- the solution is then cooled to 10-15° C. to prevent precipitation of the iron complex.
- 12 M sodium hydroxide solution is slowly added to the tartrate-ferric acid under controlled conditions to prevent the temperature from rising over 20° C.
- the solution color shifts from reddish-brown to yellowish-green, signifying the formation of the FeTNa complex.
- the remaining sodium hydroxide may be added without regard to temperature.
- Sodium tartrate is added at the end to ensure long-term stability of the solution.
- Pulping conditions using an FeTNa pulping reagent are generally basic and may be carried out at pH above 12, or above 13, or at a pH of about 14 in a closed reaction vessel. Reactions carried out using FeTNa pulping reagent at a pH of 14 in a closed reaction vessel kept at 4° C. successfully dissolved cotton feedstock. Carrying out the pulping reaction in an inert atmosphere is generally preferred, and circulating an inert gas such as argon through the pulping solution prior to and during addition of pretreated feedstock may improve dissolution rates, yields, or both.
- an inert gas such as argon
- zinc-containing reagents such as Zincoxen solutions may be used as pulping reagents.
- the active ingredients of the zincoxen solution are zinc oxide (ZnO) and EDA.
- Zincoxen solutions may be prepared according to the procedures published by Shenouda and Happey (S. G. Shenouda and F. Happey, European Polymer Journal 12 (1975) 289) or Saxena, et al. (V. P Saxena, et al., Journal of Applied Polymer Science 7 (1963) 181). Ethylenediamene-water solutions are chilled to 0° C. followed by stirring in zinc oxide powder. Continuous stirring for 72 hours while maintaining the temperature at 0° C. produces a suitable Zincoxen solution.
- Pulping conditions using a Zincoxen pulping reagent are generally basic and may be carried out at pH above 12, or above 13, or at a pH of about 14 in a closed reaction vessel.
- residence times of up to 4-48 hours in the pulping stage are suitable to dissolve and promote molecular separation of cellulose molecules present in the treated cellulose-containing feedstock.
- the pulping stage takes place in a closed chamber and an inert gas, such as nitrogen or argon, is introduced in the airspace to inhibit or prevent oxidation of pulping solution constituents. Oxygen-containing gases may be substantially evacuated from the pulping stage.
- agitation of the pulping mixture, mixing of the pulping mixture, or both may be provided; in some embodiments, an inert gas, such as nitrogen or argon, may be bubbled through the pulping mixture prior to pulping, during pulping, or both.
- the cellulose molecules are substantially isolated and may be fully or partially dissolved to form substantially linear cellulose chains in the pulping stage, depending on the reagent used and the residence time.
- the pulping solution is filtered, following a suitable residence time, to remove non-cellulosic constituents with the solution and isolate substantially purified cellulose polymers, which are typically suspended in a viscous media. Filtration may involve multiple stages, including an optional centrifugation stage and one or more size exclusion filtration stages. A final filtration stage using pore sizes of 1 micron or less may be employed.
- the isolated, substantially purified cellulose polymers may be used in a wide range of downstream applications (See, e.g., FIG. 1 ) and, in particular applications, are used in fiber production applications to produce regenerated cellulosic fiber (See, e.g., FIGS. 2-7 ).
- the conditions of the pulping stage and the composition of the fabric feedstock are important factors in determining whether a cotton-like fiber or rayon is produced form the pulped cellulosic materials in subsequent processing.
- Full dissolution of the cellulosic fibers is generally desirable for the production of rayon-like fibers, cotton-like fibers and other regenerated cellulosic fibers.
- Suitable solvent concentrations, reagent to feedstock ratios, residence times, and the like, may be determined using routine experimentation. While Schwiezer's Reagent and the other iron- and zinc-containing pulping reagents described above are suitable pulping solvents for many applications, it will be appreciated that other pulping reagents may be available, or may be developed, and would be suitable for use in the processes described herein.
- energy is introduced to the pulped solution during a desired degree of pulping, following a desired degree of pulping, or both.
- mechanical energy, electrical energy, such as radio frequency energy, or both may be introduced during or following pulping to enhance separation of different components and promote sedimentation of heavier components.
- suitable filtration, screening exclusion treatment, size exclusion treatment, the like, or combinations or multiples thereof may be performed, during or following pulping, to remove non-organic materials (e.g., buttons, fasteners, zippers, etc.), as well as impurities and non-cellulosic materials from the fiber pulp solution.
- Suitable f filtration, screening exclusion treatment, size exclusion treatment, the like, or combinations or multiples thereof, will depend on the types and level of contaminants remaining in the fiber pulp solution. Filtration may involve scraping the top of the reaction vessel, the bottom of the reaction vessel, or both, to remove floating or sinking debris; simple size exclusion filtration; gravitation separation or centrifugation to separate solids from the dissolved cellulosic materials; the like, or combinations or multiples thereof. In some embodiments, a cascade of progressively smaller pore size filtration stages may follow preliminary separation by gravitation or centrifugation.
- Separated by-products may be isolated and purified (if appropriate) for re-sale or distribution to secondary markets.
- the pulping solution may be optionally treated with glycerin or glycerol or another agent to impart softness to the texture of the fiber.
- isolated cellulose molecules may be extruded to form regenerated fibers and textile materials.
- the isolated cellulose molecules are generally filtered or otherwise separated, and may be acidified and processed in a wet extrusion stage to precipitate cellulose fibers and produce cotton fibers, rayon fibers, or a mixture of cotton and rayon fibers.
- Various acids may be used in this precipitation stage, such as sulfuric, citric or lactic acids.
- a sulfuric acid bath is used in combination with a wet extrusion process, wherein the viscous cellulose polymer solution is pumped through a spinneret, and the cellulose is precipitated to form fibers as it contacts the acid bath.
- the extrusion process, system, or both may be modified and adjusted to produce fibers having different lengths, diameters, cross-sectional configurations, durability, softness, moisture wicking properties, and the like.
- the newly formed fibers are stretched, blown, or both, to produce desired configurations, washed, dried, and cut to the desired length.
- Closed vat, continuous fiber extrusion techniques may be used. Closed vat systems allow recovery, recycling, or both, of any produced gases and by-products.
- Using fiber extrusion techniques is highly advantageous when applied to the regeneration of cellulosic materials to produce cotton fibers, rayon fibers, or both, since it allows a high degree of custom design and engineering of cellulosic fibers to achieve targeted comfort and performance characteristics (e.g., fiber length, diameter, cross-sectional shape, durability, softness, moisture wicking, etc.).
- Naturally grown fibers cannot be produced in desired or specified fiber lengths, diameters, cross-sectional profiles, or the like and cellulosic fibers regenerated using this process may therefore have different, and superior, properties compared to the natural fibers present in the initial recycled fabric feedstock.
- fiber extrusion may produce fibers having a denier of from about 0.1 to 70 or more denier.
- fiber extrusion may involve extruding multifilaments having from about 20 to 300 single monofilaments, each having a denier of from about 0.1 to about 2. Extruding fine denier filaments produces woven fabric that feels softer to the touch and is desired in many embodiments.
- fiber extrusion may additionally involve adding a false twist to the extruded filaments and texturizing them to resemble spun yarn. These treatments may obviate the necessity of using opening and spinning processes to produce yarn from the extruded fibers. Further handling of the fibers may involve cutting the continuous fiber to specific uniform lengths (stapling), missing, opening, carding, drawing, rowing, spinning, etc.
- waterless dyeing techniques may be used to further reduce the environmental impact of the overall process.
- Waterless dyeing technologies are available and typically use supercritical carbon dioxide as a solvent and carrier for dyestuff.
- color treatment of regenerated fibers may involve determining the absorbency of the regenerated fiber and determining the color properties of fibers using spectrophotometric techniques. Color signatures and dye formulations may then be customized according to the specific properties of regenerated fibers to eliminate differences in coloration that may result from different batch qualities.
- regenerated fibers or yarns may be surface treated (e.g., using a bleaching composition) and then dyed or overprinted using, for example, reactive, direct, pigment, sulfur, vat dye types and prints, the like, or combinations or multiples thereof.
- all fiber regeneration process steps, from garment reclamation to fiber extrusion may be located at a common geographic site (or at nearby sites). For some purposes, it may be desirable to locate different stages of the process at different physical locations. It may be desirable, in some applications, for example, to locate garment reclamation sites in populous areas, while locating other processing facilities and, in particular, the wet extrusion facility, in locations proximate textile processing facilities—e.g.
- garment reclamation and initial processing may take place at one location and cellulosic pulp may then be shipped or transported to a different location for wet extrusion and other downstream processing (e.g., dying, garment manufacturing, etc.).
- Regenerated cellulosic fibers (e.g., cotton, rayon, or both) produced as described above may be twisted into thread, dyed, bleached, woven into textiles and, ultimately, cut and sewn into garments.
- low grade natural cotton fibers e.g., low staple length cotton fibers
- low grade natural cotton fibers may be pulped as described herein, and then acidified and subjected to a wet extrusion process to produce newly formed fibers which may be stretched, blown, or both, to a desired diameter, cross-sectional profile or the like, washed, dried, and cut to a desired length.
- low grade (natural, recycled, or both) cotton fibers may be regenerated and converted to newly formed, higher value fibers having more desirable properties than those of the original natural cotton fibers, recycled cotton fibers, or both.
- FIG. 8 shows a schematic flow diagram illustrating the processing of a blended textile input according to methods described herein.
- blended textile input is separated into cotton-heavy and polyester-heavy blends during one or more sorting and pretreatment step(s).
- the constituent cotton and polyester polymers in each of the separated stages are dissolved and isolated to produce “liquefied” cellulose (from the cotton-heavy feedstock) and “liquefied” polyester from the polyester-heavy feedstock.
- These isolated cellulosic and polyester materials may be extruded into regenerated fibers, as desired, or used for other downstream applications.
- the undissolved, non-cellulosic constituents remaining after dissolution of the cotton-heavy blend feedstock may be treated for dissolution of polyester to produce liquefied polyester.
- the undissolved, non-polyester constituents remaining after dissolution of the polyester-heavy blend feedstock may be treated for dissolution of cellulose to produce a liquefied cellulose.
- Undissolved components such as other fibers, zippers, buttons, and the like, may be collected and re-used or discarded.
- FIG. 10 shows a schematic flow diagram outlining process steps as disclosed herein for producing paper or packaging materials from a combination pulp including a textile pulp and a wood pulp.
- a textile pulp i.e., pulp made or derived from textiles, as discussed above, which includes cellulosic material and can also include non-cellulosic material
- wood pulp can be mixed with wood pulp to form a combination pulp used to develop packaging material (e.g., cardboard boxes, corrugated cardboard, cardboard liner, or components of a cardboard box), paper products (e.g., toilet paper, paper towels, wet wipes, printer paper, or the like), or the like. Therefore, recycled textiles can be used to obtain a first pulp which is mixed with a second pulp derived from a wood pulping process.
- Wood pulp includes three components: cellulose, hemicellulose, and lignin.
- the percentage of the components can be affected by type of wood (e.g., hard vs. soft), climate (e.g., temperate), the like, or combinations thereof.
- Cellulose maintains the strength in wood fiber due, at least in part, to the high degree of polymerization and linear orientation of the cellulose.
- Hemicellulose acts as the matrix.
- Lignin acts as the glue, thereby holding the fibers together and the cellulose together within the fiber cell wall.
- the wood can be processed to obtain pulp having a cellulose content based on the subsequent use.
- Wood pulp can be formed by any appropriate process or system, including, for example, mechanically, chemically, thermochemically, chemi-thermochemically, the like, or combinations or multiples thereof.
- a first wood pulp having the highest cellulose content can be used to form textile fibers, derivatized celluloses, cellulose ethers, or the like.
- a second wood pulp having an intermediate cellulose content e.g., 20-45%
- a third wood pulp having the lowest cellulose content e.g, ⁇ 10%) can be used to form cardboard.
- the textiles Before textile pulping, during textile pulping, or after textile pulping, the textiles can undergo additional processing to change a size characteristic or parameter of a textile fiber or cellulose fiber derived from processing the textile.
- the textiles whether as a pulp or otherwise, can be processed with a Tornado pulper, a refiner, a valley beater, the like, or combinations or multiples thereof.
- the size characteristic or parameter of the textile fiber or cellulose fiber derived from processing the textile can be the same as or substantially the same as (i.e., ⁇ 20%) as a size characteristic or parameter of the wood pulp fibers (e.g., average size of textile fiber or cellulose fiber is within a 20% difference of an average size of fibers of the wood pulp).
- the size characteristic or parameter of the textile fiber or cellulose fiber derived from processing the textile can be reduced to prevent a paper or cardboard production machine from jamming, malfunctioning, or the like due to the excessive size of the textile fiber or cellulose fiber derived from processing.
- a textile fiber or cellulose fiber derived from processing the textile can have a length of 4-8 millimeters (mm). The length of the textile fiber or cellulose fiber can be reduced to, for example, 0.5 to 4 mm by undergoing the additional processing.
- a textile fiber or cellulose fiber derived from processing the textile can have a weight of 2.2-2.5 Deniers per filament (Dpf). The weight of the textile fiber or cellulose fiber can be reduced to, for example, 0.5 to 1 Dpf by undergoing the additional processing.
- Dpf Deniers per filament
- the textile pulp and the wood pulp can be mixed by any appropriate process or system, including, for example, two pipes flowing into a single pipe, adding the different pulps to a single vessel for blending, the like, or combinations or multiples thereof.
- Mixing the textile pulp with the wood pulp can increase yield by combining a lower cellulose content pulp (i.e., wood pulp) with a higher cellulose content pulp (i.e., textile pulp).
- typically discarded wood pulp components, such as lignin can be retained in wood pulp, thereby reducing cost, increasing yield, or the like.
- lignin can be burned off with the resulting steam used to generate energy. In doing so, the volume of the pulp is reduced and an additional step is required.
- retaining the lignin increases the mechanical stress (e.g., compression, tension, shear, bending, torsion, fatigue, the like, or combinations of multiples thereof) capability of the resulting product, whether paper, cardboard, or the like.
- the amount of textile pulp and the amount of wood pulp can be adjusted to form a combination pulp having the desired cellulose content.
- the ratio, as a percentage, of textile pulp and wood pulp in the combination pulp can range from 0.1:99.9 up to at least 55:45, including, for example 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, and the like.
- 150 kg of a wood pulp having 4% cellulose can be combined with 8 kg of a textile pulp having 90% cellulose to form a combination pulp having a cellulose content of 8.35%, such as for developing cardboard.
- 150 kg of a wood pulp having 15% cellulose can be combined with 120 kg of a textile pulp having 75% cellulose to form a combination pulp having a cellulose content of 41.67%, such as for forming paper products.
- the textile pulp can also include non-cellulose material, such as a polyester, nylon, rayon (or Lyocell), acrylic, the like or combinations or multiples thereof.
- the non-cellulose material can increase the mechanical stress (e.g., compression, tension, shear, bending, torsion, fatigue, the like, or combinations of multiples thereof) of the resulting product, e.g., paper product or cardboard.
- non-cellulose material can be added to the textile pulp, the wood pulp, the combination pulp, or combinations thereof to increase the mechanical stress of the resulting product.
- the processing steps used to form the textile pulp, the textiles, fibers, or derivatives thereof can be adjusted based on the resulting product to be developed.
- a bleaching step e.g., bleach intensity, number of bleaching steps or sub-steps, or the like
- a sorting step can be less thorough (e.g., instead of separating recycled textiles in bins based on increments of 2-3% cellulose content, the recycled textiles can be separated into bins based on increments of 10-15% cellulose content).
- textile pulp is discussed in reference to the combination pulp, the textile pulp can be further processed by one or more dissolving steps, as discussed above, before forming the combination pulp, when it is necessary or desirous to do so.
- a small scale experiment was conducted to establish feasibility of cellulose pulping and fiber regeneration using shredded cotton garment material as a feedstock.
- the shredded feedstock material was treated with Schweizer's Reagent to form a dissolved pulping solution, and the pulp solution was acidified by treatment with sulfuric acid. Fibers were regenerated as a result of the acidification.
- chemical reaction (1) may be omitted when using copper hydroxide and ammonia reactants to form Schweitzer's reagent as follows: Cu(OH) 2 +4NH 3 +2H 2 O ⁇ [Cu(NH 3 ) 4 (H 2 O) 2 ] 2+ +2OH
- This alternative chemistry does not require filtration (setp 5, above) and produces no by-products that require disposal or removal.
- FIG. 9A shows a magnified image of a regenerated cellulosic fiber produced as described above (on the left, labeled Evmu) and FIG.
- FIG. 9B shows a magnified image of a premium long-staple cotton fiber as tested in Harzallah, Benzina & Drean, 2009 (right-side image, labelled “cotton,” reproduced without permission from aforementioned paper).
- the comparative fiber properties of the regenerated cellulosic fiber produced as described above and the premium long-staple cotton fiber, as reported in the above-mentioned literature reference, are outlined below.
- FIG. 9C shows a magnified cross-sectional image of a regenerated cellulosic fiber produced as described above. Extrusion allows for precision control and consistency in fiber cross-section and length. Regenerated cellulosic fibers produced as described herein may be extruded under various conditions and to produce different fiber cross-sectional profiles and lengths. In general, regenerated cellulosic fibers produced herein may be extruded just as other manmade fibers and can be prepared as mono, multifilament or stapled in desired length for ring/OE spinning.
Abstract
Description
- This application claims the benefit of pending U.S. Provisional Patent Application No. 63/036,856, filed Jun. 9, 2020. The contents of which are herein incorporated by reference in their entirety.
- The present disclosure relates to methods and systems for processing cellulose-containing materials such as textiles, including textile garments (used and un-used) and scraps, biomass, wood pulp, and the like and for isolating cellulose molecules for use in a variety of downstream applications. In particular applications, the present disclosure relates to methods and systems for treatment of cellulose-containing materials to isolate cellulose molecules and to produce regenerated polymers, fibers, fabrics, the like, or combinations or multiples thereof from the isolated cellulose molecules. Recycling and regeneration of textiles is described in detail and provides significant social, environmental and economic benefits.
- Global sales of apparel are estimated to have exceeded $1 trillion in 2011, and some estimate that over 85% of the garments purchased are discarded in a landfill within one year. This cycle wastes valuable materials and the considerable resources required to produce them, and it exacerbates waste disposal issues.
- Cotton clothing is estimated to represent about 35% of the total apparel market. Cotton fibers are composed of cellulose, a naturally occurring polymer found in all plants, wood, and natural fibers. Cotton fibers are harvested from cotton plants and consist of long, interwoven chains of cellulose polymers. These fibers are spun into thread or yarn, dyed, and ultimately woven, knit, and assembled into textiles. Natural fibers, including cotton, have a generally high and variable raw material cost due, in part, to natural disasters and climate unpredictability, regional socio-economic and political instability, human rights issues, and resource requirements.
- Growing and harvesting cotton fibers is resource-intensive. It is estimated, for example, that over 700 gallons of water are required to grow enough cotton to produce one pound of fiber. Growing cotton frequently involves heavy pesticide use, significant land resources, and produces significant levels of heat-trapping gases. Considerably more land is required for growing organic cotton than for growing “conventional” cotton. With demand for agricultural land use increasing and fresh water supplies decreasing, the cost of producing natural cotton is increasing. At some point, the current scale of cotton production may become unprofitable and unsustainable.
- Cotton has been recycled to provide raw material for paper pulping plants. Re-processing methods that convert used cotton into rags, mattress ticking, seat stuffing, insulating materials, and the like are also available, but these processing methods have been adopted in limited applications because the value of the converted material is relatively low.
- In contrast to cotton, which is a natural fiber, rayon fibers are manufactured from wood pulp using the viscose process. In this process, purified cellulose is solubilized and then converted or regenerated into cellulose fiber. This process requires steeping, pressing, shredding, aging, xanthation, dissolving, ripening, filtering, degasing, spinning, drawing and washing. This process is time sensitive, requires multiple chemical treatments, produces lignin and other waste from unusable wood material and is, at best, a semi-continuous manufacturing process.
- The present disclosure is directed to providing systems and methods for processing cellulose-containing feedstocks, such as recycled fabric, fabric scraps and other cellulose containing materials, many of which would otherwise be wasted or used to produce low value products, to isolate their constituent cellulosic polymeric structures. The polymeric cellulosic structures are then used in industrial processes such as fabric production. Implementation of the disclosed processing schemes with a variety of garment/fabric feedstock materials may produce regenerated fibers and textile products having improved, customizable, or both properties using processes having low environmental impacts.
- Methods and systems of the present disclosure relate to processing of cellulose-containing materials including, for example, postconsumer cellulosic waste, cellulose-containing textiles and garments (e.g., recycled or used or waste textiles and garments), virgin cotton, wood pulp, biomass, and the like, to produce isolated cellulose polymers for use in downstream processing applications. In some embodiments, cellulose-containing materials used as raw feed material for processing comprise discarded garments, scrap fabric materials, or both, and processing produces isolated cellulose polymers that can be further processed and extruded to provide regenerated fibers having improved, customizable, or both properties for use in textile industries or for other purposes.
- A multi-stage process is described, incorporating one or more pretreatment stages providing removal of contaminants and preparation of cellulosic materials, followed by pulping, molecular separation of cellulose polymers, or both. In some embodiments, the pretreatment and pulping processes may be carried out in a continuous, semi-continuous or batch system. In some embodiments, the pretreatment and pulping processes may be carried out in one or more closed reaction vessel(s), and processing reagents may be recovered and re-used or processed for other uses.
- Numerous pretreatment processing stages are described and may be used alone or in combination to remove non-cellulosic constituents of the feed and prepare cellulosic components for pulping and dissolution. Pretreatment is followed by at least one cellulose pulping or dissolution stage that promotes the molecular separation and isolation of cellulose polymers, such as by disrupting intermolecular hydrogen bonds. In some embodiments, cellulosic polymers isolated during the pulping stage, the dissolution stage, or both, are substantially thermoplastic and are moldable when energy (e.g., heat below the char point) is introduced to the system.
- Isolated cellulose polymers produced using the processes described herein may be used in a variety of downstream applications, as described in more detail below and, in some embodiments, may be extruded to form regenerated cellulosic fibers. In some aspects, isolated cellulose polymers may be re-generated to provide longer chain polymers and fibers (or polymers and fibers having other desirable characteristics different from the characteristics of the cellulose-containing feedstock) that are useful in various industrial processes, including textile production. In addition to employing a raw feedstock materials that are typically discarded (wasted, at a cost), processing steps having generally low environmental impacts are preferred.
- In one aspect, methods and systems of the present disclosure provide a closed-loop garment recycling process that transforms reclaimed garments and textiles into high-quality, bio-based fiber for use in creating new textiles, apparel, and other fiber-based products. Used and waste garment collection, sorting, transport and processing may all be involved as part of a closed loop process. Retail enterprises (and others) may serve as collection stations and may offer incentives, rewards, or the like for donations. Further garment processing may take place at the donation site or at one or more remote sites. Cotton, cotton-like regenerated fabrics, rayon and other fibers may be produced using the reclaimed garments and textiles.
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FIG. 1 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to liquefied cellulose suitable for use in a variety of downstream applications. -
FIG. 2 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber and incorporating one or more of a variety of pretreatments. -
FIG. 3 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating a high temperature aqueous or supercritical carbon dioxide pretreatment step and incorporating optional additional treatment steps. -
FIG. 4 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating a combination of pretreatment steps. -
FIG. 5 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating another combination of pretreatment steps. -
FIG. 6 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating another combination of pretreatment steps. -
FIG. 7 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for converting cellulose-containing materials to regenerated cellulosic fiber incorporating yet another combination of pretreatment steps. -
FIG. 8 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for processing blended textile input to produce liquefied cellulosic and polymeric output. -
FIG. 9A shows a magnified image of a regenerated cellulosic fiber produced as described herein;FIG. 9B shows a magnified image of a premium long-staple cotton fiber as tested in Harzallah, Benzina & Drean, 2009; andFIG. 9C shows an enlarged, cross-sectional view of a regenerated cellulosic fiber produced as described herein. -
FIG. 10 illustrates an exemplary schematic flow diagram outlining process steps as disclosed herein for producing paper or packaging materials from a combination pulp including a textile pulp and a wood pulp. - It will be understood that the appended drawings present many alternatives and various specific embodiments, and that there are many variations and combinations of processing steps, as well as additional aspects of systems and methods of the present invention. Specific process design features may be modified and used in different combinations, for example, for use in various intended applications and environments.
- In one aspect, systems and methods disclosed herein process cellulose-containing materials to produce isolated cellulosic polymers suitable for use in downstream processing and a variety of downstream applications and production pathways. Cellulose-containing materials that are useful as raw materials for this process include a wide range of materials, such as cellulose-containing postconsumer waste, biomass materials and pulp (e.g., wood pulp), cotton and cotton-containing materials, and the like, including unworn or worn and discarded cotton and cotton-containing apparel, as well as scrap cotton fiber and fabric. The cellulose-containing feedstock undergoes at least one pretreatment stage (and optionally multiple pretreatment stages) and at least one pulping or dissolution stage to produce isolated cellulose molecules suitable for use in various different application pathways.
- The raw cellulose-containing feed material may be substantially homogeneous (e.g., pre- or post-consumer waste, scrap textile fiber and fabric, cotton-containing fabrics, biomass or pulped wood or biomass, etc.), or it may be at least somewhat heterogeneous (e.g., cellulose-containing materials from mixed sources and of mixed types). When post-consumer textile materials are used as feedstock, used clothing collection and sorting may be accomplished via clothing retailers, manufacturers, recyclers, and various other organizations, providing access to large volumes of used, cellulose-containing garments and scrap materials that would otherwise be discarded. Depending on the type and homogeneity of the cellulose-containing feedstock, optional sorting and removal of non-cellulosic components may be carried out prior to pretreatment of the cellulose-containing feedstock.
- When reclaimed garments and textiles are used as cellulose-containing feed material, initial sorting of reclaimed garments and textiles according to fiber content may be advantageous prior to feedstock pretreatment and dissolving. In some embodiments, for example, reclaimed material (e.g., garments and textiles) may be sorted by cellulosic content—e.g., reclaimed materials may be separated into groups having different cellulosic contents, such as >90% or >80% or >70% or >50%, or other cellulosic contents, and less than 50% cellulosic content. Reclaimed fabric material having other fiber contents and compositions may also be sorted and separated, and reclaimed material may also be sorted by composition, such as separating cotton-wool blends, cotton-polyester blends, cotton-elastane blends, cotton-spandex blends, and the like. Separation of non-cellulosic-containing materials such as buttons, zippers, and the like may take place at the time of or following sorting and process pretreatment. Likewise, mechanical sizing or comminution, such as shredding, pulling, grinding, cutting, tearing, and the like may take place prior to or following sorting and process pretreatment.
- Cellulosic feedstocks such as reclaimed garments and textiles typically incorporate a variety of dyes, chemical finishes, or both, and may be contaminated with other materials, such as dirt, grease, and the like. Other types of cellulosic feedstocks, such as biomass, postconsumer waste, and the like, also contain contaminants that are desirably removed prior to a pulping stage. Raw cellulose-containing feedstock (optionally treated to remove non-cellulose-containing materials, and optionally sized) is typically processed in one or more pre-treatment stage(s) to remove dyes, finishes, contaminants (oils, grease, etc.) and the like from the feedstock. Cellulosic feedstocks including textile materials may optionally be mechanically treated to provide smaller sized, or more uniformly sized, feedstock. The fabric feedstock may be sized if desired, such as by shredding, to provide a sized feedstock having a fragmented, high surface area for fiber pulping. Feedstock sizing is typically accomplished using mechanical cutting, shredding, or other mechanical size reduction techniques. Processing to remove non-cellulosic components, such as buttons, zippers, fasteners, and the like may take place, if desired, prior to pretreatment, following pretreatment, or both.
- Several different pre-treatment stages are described below, and various combinations of pretreatment stages may provide benefit, depending on the nature of the cellulosic feedstock. Depending on the properties of the raw textile feedstock, one or more of the pretreatments may be used, alone or in combination with other pretreatments. Several (optional) pre-treatment stages are described below, and several advantageous pre-treatment combinations are also described. It will be appreciated that additional pre-treatments may be used in combination with the pre-treatments described, and that various specific combinations other than those specifically illustrated and described may be used.
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FIG. 1 illustrates an overall process flow diagram for treating cellulose-containing materials to produce isolated cellulose polymers, identified inFIG. 1 as “Liquefied Cellulose,” suitable for use in a variety of downstream applications, such as fiber production (e.g., textiles, technical fibers and geo-textiles), production of other extrusion manufacturing methods, constructional manufacturing methods (e.g., 3D printing media, membranes, injection molding media), or both, use as a chemical feedstock for production of biofuels, lubricants and other chemical manufacturing, and for use as food additives, in films, coating, fillers, membranes, packaging, construction materials, non-woven materials, and the like.FIG. 2 illustrates an overall process flow diagram for treating cellulose-containing materials to produce liquefied cellulose suitable for fiber extrusion and including additional processing stages for production of regenerated cellulosic fiber. The cellulose-containing materials may undergo similar pretreatment and the pulping stage, the dissolution stage, or both, as illustrated inFIGS. 1 and 2 , while the isolated cellulose product may be used for different applications, as shown. - In general, cellulose-containing feed materials may undergo optional feedstock preparation stages, such as feedstock sorting, removal of non-cellulosic components, or both. The cellulose-containing feedstock then undergoes at least one pretreatment stage, followed by pulping or, dissolution of, or both, the pretreated cellulose-containing feedstock and filtration to produce isolated cellulose polymers. Several pretreatment stages are described below and are illustrated in the accompanying diagrams. Depending on the composition of the cellulose-containing feedstock and the attributes of the cellulosic product desired, one or more than one of the pretreatment stages may be used alone or in combination with other pretreatment stages. Specific combinations of pretreatments that may be useful in particular applications are described in greater detail below with reference to
FIGS. 3-7 . Each of the pretreatment stages is described in more detail below. - In one embodiment, methods disclosed herein provide pretreatment of cellulose-containing feed materials using a high temperature aqueous washing process. This pretreatment stage is particularly useful for pretreatment of cellulose-containing feed materials comprising recycled garments and may facilitate removal of contaminants such as soils, deodorants, lanolin, silicone and cationic softeners from the feedstock, as well as stripping various fabric treatments, such as optical brighteners, moisture wicking enhancers, and the like, from the feed material. Aqueous media maintained at a temperature above 100° C., optionally above the boiling point of the aqueous media, generally above 120° C., often between 120° C. and 170° C., sometimes between 130° C. and 150° C., and up to 200° C., may be used. In some embodiments, the high temperature aqueous washing pretreatment stage is conducted in a closed vessel batch system with circulation or agitation or mixing of the hot aqueous media. Pressure conditions in a closed vessel system, as described, may range from about 100 kPa to about 2000 kPa, depending on the temperature of the aqueous media, with higher pressure conditions accompanying higher temperature media.
- Aqueous media used in a high temperature pretreatment stage may comprise water alone, or it may comprise an aqueous solution having one or more additives. In some embodiments, the aqueous media may comprise water enriched with ozone. In some embodiments, the aqueous media may comprise water enriched with oxidative agents such as hydrogen peroxide or sodium perborate. In additional embodiments, surfactants (e.g., Sodium stearate, Fatty Alcohols, 4-(5-Dodecyl) benzenesulfonate, Alcohol ethoxylates and the like), various hydroxide compositions (e.g., Ca, Mg, Na, K, and Li hydroxides), the like, or combinations or multiples thereof, may be mixed and circulated with the aqueous media in a high temperature aqueous pretreatment stage and may act as wetting agents. In some embodiments, the high temperature aqueous washing stage incorporates an aqueous solution comprising NaOH at a concentration of from about 1% to about 15%, at a pHin excess of about 11, and in some embodiments in excess of about 12. Residence times are sufficient to substantially remove impurities from the cellulose-containing feedstock.
- The aqueous wash solution may be evacuated following a suitable residence time. In some embodiments, multiple aqueous washing stages may be implemented, using the same or different aqueous solutions, all at high temperature and pressure conditions. Optional rinsing of the solids with an aqueous solution may be implemented following evacuation of the wash solution. Rinsing may take place at ambient temperatures and pressures, with optional agitation and mixing, and the rinse solution is removed following a suitable residence time. Cellulose-containing treated solids may undergo one or more additional pretreatment stage(s) or may be further processed in a pulping stage, a dissolution stage, or both.
- In some embodiments, a water-less pretreatment, “non-toxic” pretreatment, or both, may be used to remove contaminants such as dyes, finishes, surface impurities and other contaminants from cellulose-containing feed materials, and particularly from feed materials comprising recycled garments or textiles. In this treatment stage, cellulose-containing feed material may be introduced to a closed and pressurized chamber, where the feed material contacts supercritical carbon dioxide, alone or in combination with additional reagent(s). In some embodiments, the supercritical CO2 may be enriched with ozone. In some embodiments, the supercritical CO2 may enriched with oxidative agents such as hydrogen peroxide or sodium perborate. In additional embodiments, surfactants (e.g., Sodium stearate, Fatty Alcohols 4-(5-Dodecyl) benzenesulfonate, Alcohol ethoxylates and the like) may be mixed and circulated with the supercritical CO2 in a pretreatment stage. Following a suitable residence time, supercritical carbon dioxide containing dissolved contaminants is withdrawn to a separator, where the carbon dioxide may be decompressed and returned to a gaseous state, while the contaminants may be collected and removed. The gaseous carbon dioxide may be recycled in a closed loop process and re-used for additional pretreatment cycles. Cellulose-containing treated solids may undergo one or more additional pretreatment stage(s) or may be further processed in a pulping stage, a dissolution stage, or both.
- In some embodiments, cellulose-containing feedstock, cellulose-containing treated solids, or both, are treated, prior to pulping or dissolution, with a high temperature (>320° C.), high pressure (>2.5 Mps) aqueous treatment, in a closed and substantially rigid reaction vessel. This pretreatment stage promotes breakdown of the crystalline structure of cellulose and facilitates modification of cellulosic constituents to an amorphous, non- or less-crystalline structure that is more amenable to pulping, dissolution, or both.
- In some embodiments, a pretreatment stage involves exposing the cellulose-containing feed material (or cellulose-containing treated solids, or both) to a “bleaching” agent, such as an oxidative or reducing agent, typically in an aqueous solution, at an oxidative/reducing agent concentration and for a residence time sufficient to remove materials such as dyes, finishes, and other contaminants from the cellulosic feedstock. Suitable oxidative agents, reducing agents, or both, include, for example, peroxide compositions (e.g., H202, Na2O2) and perborate (e.g., NaBO3) compositions. Additional oxidative agents, reducing agents, or both, that may be used in pretreatment stages as described herein include one or more of the following compositions: per carbonate compositions; sodium carbonate; per acetic acid compositions; potassium permanganate; persulfate compositions; ozone; sodium chloride; calcium oxychloride, sodium hypochlorite; calcium hypochlorite; lithium hypochlorite; cloramine; isocynual trichloride; Sulphur dioxide; sodium hydrosulfite; sulphoxylates; acidic sodium sulphite; sodium bosulphite; sodium meta bisulphite; TAED (tetra-acetyl-ethylene-diamine); and sodium hydrosulfite.
- In some embodiments, bleaching agent treatment may involve treatment in an aqueous solution of calcium hypochloride (bleach powder) or sodium hypochlorite (NaOCl) in combination with sodium carbonate (soda ash) at a pH in excess of 8 and, in some embodiments, at a pH in excess of 9. Agitation or mixing of the materials in the bleaching agent pretreatment stage may be provided, and treatment with an oxidative, a reducing agent, or both, may take place in a closed reaction vessel.
- The bleaching agent solution may be evacuated following a suitable residence time and optional rinsing of the solids with an aqueous solution may be implemented. Aqueous rinsing may take place at ambient temperatures, with the rinse solution removed following a suitable residence time. The bleaching agent may be neutralized, following this treatment, by introduction of a weak acid such as hydrogen peroxide. In some embodiments, multiple bleaching agent treatment cycles may be implemented using different oxidative or reducing reagents to treat the solids at different concentrations, pH conditions, temperature, residence times, the like, or combinations or multiples thereof, as appropriate. Recycling and regeneration of the oxidative or reducing agent(s) may be incorporated in the process, as is known in the art. Introduction of other weak acids may be effective to reduce the pH of the treated, cellulose-containing solids, if desired, following optional rinsing steps.
- In some embodiments, methods disclosed herein provide pretreatment of cellulose-containing feed materials (or cellulose-containing treated solids, or both) by exposure to aqueous media containing one or more organic solvents. Suitable organic solvents may be selected from the group consisting of: acetic acid; acetone; acetonitrile; benzene; 1-butanol; 2-butanol; 2-butanone; t-butyl alcohol; carbon tetrachloride; chlorobenzene; chloroform; cyclohexane, 1,2-di chloroethane; diethylene glycol; di ethyl ether; diglyme (diethylene glycol dimethyl ether); 1,2-dimethoxy-ethane (glyme, DME); dimethyl formamide (DMF); dimethyl sulfoxide (DMSO); 1,4-dioxane; ethanol, ethyl acetate; ethylene glycol; glycerin; heptane; hexamethylphosphoramide (HMPA); hexamethylphosphorous tramide (HMPT); hexane; methanol; methyl t-butyl ether (MTBE); methylene chloride; nitromethane; pentane; 1-propanol; 2-propanol; pyridine; tetrahydrofuran (THF); toluene; triethyl amine; a-xylene; and m-xylene. The aqueous media containing organic solvent(s) is generally maintained at a basic pH, generally at a pH in excess of 9, and often at a pH of 10 or above. Treatment with organic solvents may be achieved using high temperature or cooler aqueous media.
- In some embodiments, methods disclosed herein may optionally employ enzymatic treatment to shorten cellulose molecules, increase cellulose solubility, reduce reaction times, or both, in subsequent treatment stages. Suitable enzymes may include endogluconases (e.g., Cel 5A, Cel 7B, Cel 12A, Cel 45, Cel 61A); Cellobiohydrolases (e.g., Cel 6A, Cel 7A); LPMO/GH6 l; cellulases; and the like. In general, temperatures of from about 30° to 90° C., pH between about 4 to about 9 and dwell times of from about 20 min to 48 hours may be suitable for enzymatic treatment.
- Enzymatic treatment(s) involving xylanases, alkaline pectinases, lipases, esterases, the like, or combinations or multiples thereof may also be used for feedstock pretreatment prior to pulping. In yet additional embodiments, feedstock may be treated using enzymatic cultures containing biological organisms (fungi, bacteria, etc.) that secrete cellulolytic enzymes (e.g., cellulases). Enzyme cultures such as Trichoderma Reesei, Trichoderma viride, Penicillium janthinellum, Halorhabdusutahensis, A Niger, Humicola, and mixtures of such enzyme-producing cultures, are suitable. Mechanical treatments such as pulverization, emulsification treatment(s), or both, may be implemented following enzymatic treatment.
- For some applications (for example, those in which natural or light-colored or undyed regenerated fiber is desired as an end-product), optional treatment using a swelling agent, such as an ionic liquid, is employed prior to pulping to enhance the absorption of and penetration of the pulping agent. Treatment with a swelling agent (e.g. an ionic liquid) may be preceded by or implemented in combination with one or more other pretreatment stage(s). Ionic liquids may comprise hydroxides, such as Ca, Mg, Na, K, Li hydroxides, the like, or combinations or multiples thereof. Swelling agents suitable for use as reagents in a pretreatment stage may alternatively or additionally comprise one or more of the following reagents: [AMIM]Cl 1-Allyl-3-methylimidazolium chloride; [BzPy]Cl Benzylpyridinium chloride; [BMIM]Ace 1-Butyl-3-methylimidazolium acesulphamate; [BMIM]DBP 1-Butyl-3-methylimidazolium dibutylphosphate; [BMIM]Cl 1-Butyl-3-methylimidazolium chloride; [BMIM]PF6 1-Butyl-3-methylimidazolium hexafluorophosphate; [BMIM]BF4 1-Butyl-3-methylimidazolium tetrafluoroborate; [BMPy]Cl 1-Butyl-3-methylpyridinium chloride; [DBNH]AcO 1,8-Diazabicyclo[5.4.0]undec-7-enium acetate; [DBNH]EtCOO 1,8-Diazabicyclo[5.4.0]undec-7-enium propionate; [DMIM]DEP 1,3-Dimethylimidazolium diethylphosphate; [DMIM]DMP 1,3-Dimethylimidazolium dimethylphosphate; [EMBy]DEP 1-Ethyl-3-methylbutylpyridinium diethylphosphate; [EMIM]AcO 1-Ethyl-3-methylimidazolium acetate; [EMIM]Br 1-Ethyl-3-methylimidazolium bromide; [EMIM]DBP 1-Ethyl-3-methylimidazolium dibutylphosphate; [EMIM]DEP 1-Ethyl-3-methylimidazolium diethylphosphate; [EMIM]DMP 1-Ethyl-3-methylimidazolium dimethylphosphate; [EMIM]MeS04 1-Ethyl-3-methylimidazolium methanesulphonate; [HPy]Cl 1-Hexylpyridinium chloride; [E(OH)MIM]AcO 1-Hydroxyethyl-3-methylimidazolium acetate; [DBNMe]DMP 1-Methyl-1, 8-diazabicyclo[5.4.0]undec-7-enium dimethylphosphate; [P4444]0H Tetrabutylphosphonium hydroxide; [TMGH]AcO 1,1,3,3-Tetramethylguanidinium acetate; [TMGH]n-PrCOO 1,1,3,3-Tetramethylguanidinium butyrate; [TMGH]COO 1,1,3,3-Tetramethylguanidinium formiate; [TMGH]EtCOO 1,1,3,3-Tetramethylguanidinium propionate; [P8881]Ac0 Trioctylmethylphosphonium acetate; and HEMA Tris-(2-hydroxyethyl)methylammonium methyl sulphate.
- In one exemplary embodiment, cellulose-containing feed materials (or cellulose-containing treated solids, or both) may be treated with an ionic solution such as an aqueous solution comprising Ca, Mg, Na, K, Li hydroxides, the like, or combinations or multiples thereof, followed by exposure to a sodium hydrosulfite (Na2S204) reducing agent, a bleaching agent such as peroxide, perborate, persulfate, and sodium or calcium hypochlorite, or both. Small amounts of Bromium (Br) may be used as a catalyst during this treatment. This treatment is generally carried out at a pH in excess of 9, and often at a pH of 10 or 10.5 or above. Treatment with swelling agents such as ionic liquids may be achieved using high temperature or cooler aqueous wash media. In some embodiments, treatment with a swelling agent (e.g., an ionic liquid) is conducted at temperatures of 0° C. or lower, provided the aqueous solution or slurry is prevented from freezing, and provided the viscosity of the solution is maintained at an acceptable level. In some embodiments, and particularly when ionic liquids having an acetate group are used, the treatment may be carried out at an acidic pH, typically at a pH less than 6, and in some embodiments at a pH less than 5. In some embodiments, the proportion of cellulose-containing feed materials (or cellulose-containing treated solids, or both) in the ionic solution is from about 2% to about 40%; in some embodiments, the proportion of cellulose-containing feed materials (or cellulose-containing treated solids, or both) in the ionic solution is from about 5% to about 25%.
- It will be appreciated that numerous (optional) pretreatment processes are described herein and are illustrated in
FIGS. 1 and 2 . Pretreatment of cellulose-containing feedstock material, as described, may implement any of these pretreatment processes, singly or in combination with one or more other pretreatment processes. In some embodiments, carrying out elevated temperature aqueous pretreatment in a closed vessel is preferred, alone or in combination with other pretreatment stages, prior to pulping and dissolution of the cellulose polymers. In some embodiments, carrying out elevated temperature aqueous pretreatment with the use of ozone enrichment, oxidative agents, surfactants, the like, or combinations or multiples thereof is preferred, alone or in combination with other pretreatment stages, prior to pulping. In some embodiments, treatment in ionic solution followed by exposure to a reducing agent, a bleaching agent, or both, is preferred, preferably in combination with a washing step. In some embodiments, pretreatment involves elevated temperature aqueous pretreatment, followed by ionic pretreatment, followed by enzymatic pretreatment. In some embodiments, one or more of the pretreatment stages, or all pretreatment stages, are carried out a pH of at least about 9. In some embodiments, one or more of the pretreatment stages, of all of the pretreatment stages, are carried out at a pH of at least about 10. - Pretreatment preferably takes place in a closed vessel and, in batch treatment schemes, one or more pretreatment reagents may be introduced to and withdrawn from a closed vessel during various pretreatment stages, with or without intermediate rinsing or washing stages. In some embodiments, the vessel may be provided in the form of a rotating cylinder with a pressurized hull (housing) capable of withstanding pressures in the range of from 1000-5000 kPa, having inlet and outlet ports, pH and rpm control features, and having liquid agitation or circulation features. The inner reaction vessel surfaces may comprise anticorrosive metal(s) capable of withstanding concentrated acidic and alkali solutions. In some processes, both pretreatment and pulping may take place in the same vessel.
- Specific pretreatment combinations are described below with reference to the schematic flow diagrams shown in
FIGS. 3-7 . Each of these flow diagrams describes different feedstock pretreatment combinations, followed by molecular isolation and separation of cellulose polymers in a pulping or dissolution stage. Cellulose polymers may be separated from the pulping solution, such as by filtration, and regenerated cellulosic fibers may be extruded, such as in connection with a precipitation bath (e.g., an acid bath). Extruded fibers may be designed and parameters changed, depending on the type, character and physical attributes of the cellulosic fibers desired. Drying and winding produces regenerated cellulosic fibers. -
FIG. 3 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with ozone enrichment, oxidative agent(s), surfactant(s), the like, or combinations or multiples thereof. Following evacuation of the hot aqueous or supercritical CO2 media used for washing, and optional rinsing of the cellulosic solids, the cellulosic solids may optionally be treated with swelling agents (as described above), with organic solvents (again, as described above), or both. These treatment stages may be done at elevated temperatures or in cooler aqueous media. -
FIG. 4 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with oxidative agent(s), surfactant(s), or both. Following evacuation of the hot aqueous or supercritical CO2 media used for the washing stage, and following optional rinsing of the cellulosic solids, the cellulosic solids may optionally undergo enzymatic treatment as described above. The cellulosic solids may subsequently be exposed to swelling agents such as ionic liquids (e.g., NaOH) prior to a pulping or dissolution stage. -
FIG. 5 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with oxidative agent(s), surfactant(s), or both. Following evacuation of the hot aqueous or supercritical CO2 media used for the washing stage, and following optional rinsing of the cellulosic solids, the cellulosic solids may optionally be exposed to swelling agents such as ionic liquids (e.g., NaOH), followed by enzymatic treatment as described above prior to a pulping or dissolution stage. -
FIG. 6 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with optional ozone enrichment, oxidative agent(s), surfactant(s), the like, or combinations or multiples thereof. Following evacuation of the hot aqueous or supercritical CO2 media used for the washing stage, and following optional rinsing of the cellulosic solids, the cellulosic solids may optionally be exposed to swelling agents such as ionic liquids (e.g., NaOH), followed by exposure to bleaching agents, reducing agents, an enzyme treatment, the like, or combinations or multiples thereof, all as described above, prior to a pulping or dissolution stage. -
FIG. 7 illustrates treatment of cellulose-containing materials (with optional sorting and removal of non-cellulosic components) using a high temperature aqueous wash or supercritical carbon dioxide pretreatment stage in combination with optional ozone enrichment, oxidative agent(s), surfactant(s), the like, or combinations or multiples thereof. Following evacuation of the hot aqueous or supercritical CO2 media used for the washing stage, and following optional rinsing of the cellulosic solids, the cellulosic solids may optionally undergo a high-temperature, high-pressure aqueous treatment stage, as described above, to promote destruction of the cellulosic crystalline structure and favor conversion of cellulosic polymers to an amorphous phase. The cellulosic solids may be exposed to enzyme treatment, as described above, prior to a pulping or dissolution stage. - Treated cellulose-containing solids are subjected to a pulping or dissolving stage, in which the cellulose-containing solids are treated in a pulping reagent to promote molecular separation of cellulose polymers and destruction of intermolecular hydrogen bonds and other non-covalent bonds, converting cellulose-containing solids to their constituent cellulose polymers. In some embodiments, the number of intermolecular hydrogen bonds present in the cellulose polymers is reduced by at least 20% in the fiber pulping stage; in some embodiments the number of intermolecular hydrogen bonds present in the cellulose polymers is reduced by at least 50% in the fiber pulping stage; in yet other embodiments, the number of intermolecular hydrogen bonds present in the cellulose polymers is reduced by at least 70% in the fiber pulping stage. The viscosity of pulped cellulose, following the pulping treatment, is generally from about from 0.2 to as high as 900 cP, often from about 0.5 to about 50 cP.
- A variety of pulping techniques and pulping chemistries are available, and one or more of the pretreatment stages described above may be used with a variety of known pulping reagents, including those described in PCT Int'l Patent Publication WO 2013/124265 A1, the disclosure of which is incorporated herein by reference in its entirety.
- In some embodiments, copper-containing reagents are preferred for use as pulping reagents. In one embodiment, for example, Schwiezer's Reagent (the chemical complex tetraaminecopper (II) hydroxide —[Cu(NH3) 4(H20)2]) or tetraamminediaquacopper dihydroxide, [Cu(NH3) 4(H20) 2](0 H)2 is a preferred pulping agent to isolate and promote molecular separation of cellulose polymers. Schweizer's reagent may be prepared by precipitating copper(II) hydroxide from an aqueous solution of copper sulfate using sodium hydroxide or ammonia, then dissolving the precipitate in a solution of ammonia. In some embodiments, a combination of caustic soda, ammonium and cupramonium sulfate may be formulated to provide Schwiezer's Reagent.
- Solutions comprising copper(II) hydroxide and ammonia may be introduced and used in the pulping stage to form Schweizer's Reagent according to the following reaction: Cu(OH)2+4NH3+2H2O→[Cu(NH3)4(H2O)2]2++20H. In this scheme, the copper hydroxide reagent may be manufactured from recycled copper recovered, for example, from electronics and computer component waste materials. Copper hydroxide is readily made from metallic copper by the electrolysis of water using copper anodes. Ammonia may be manufactured by an innovative use of the Haber-Bosch process (3H2+N2→2NH3) capturing hydrogen from organic wastes and combining it with atmospheric nitrogen. This method may produce ammonia at low cost and eliminate greenhouse gas emissions from organic waste feedstock. Using these reagent resources and methods for generating Schweizer's Reagent, all or substantially all of the materials used in the fiber pulping process described herein (including the cellulose-containing feedstock) may be sourced as waste products, resulting in minimal or no use of nonrenewable resources.
- Other cellulose-dissolving agents may also be used in the pulping stage, such as iron-containing and zinc-containing reagents. In one embodiment, iron tartrate complex solvents (e.g., FeTNa) may be used as pulping reagents. FeTNa solutions may be prepared according to the procedure published by Seger et al. (B. Seger, et al., Carbohydrate Polymers 31 (1996) 105.) FeTNa solutions are prepared and stored while protecting them from light. The FeTNa complex may be prepared, for example, by dissolving sodium tartrate dehydrate (Alfa Assar, Cat. #16187) in deionized water, stirring and optionally heating. When the sodium tartrate dissolved, iron nitrate nonahydrate (Alfa Aesar, Cat. #12226) is added to the solution with continuous stirring. The solution is then cooled to 10-15° C. to prevent precipitation of the iron complex. 12 M sodium hydroxide solution is slowly added to the tartrate-ferric acid under controlled conditions to prevent the temperature from rising over 20° C. The solution color shifts from reddish-brown to yellowish-green, signifying the formation of the FeTNa complex. After this transition, the remaining sodium hydroxide may be added without regard to temperature. Sodium tartrate is added at the end to ensure long-term stability of the solution.
- Pulping conditions using an FeTNa pulping reagent are generally basic and may be carried out at pH above 12, or above 13, or at a pH of about 14 in a closed reaction vessel. Reactions carried out using FeTNa pulping reagent at a pH of 14 in a closed reaction vessel kept at 4° C. successfully dissolved cotton feedstock. Carrying out the pulping reaction in an inert atmosphere is generally preferred, and circulating an inert gas such as argon through the pulping solution prior to and during addition of pretreated feedstock may improve dissolution rates, yields, or both.
- In another embodiment, zinc-containing reagents such as Zincoxen solutions may be used as pulping reagents. The active ingredients of the zincoxen solution are zinc oxide (ZnO) and EDA. Zincoxen solutions may be prepared according to the procedures published by Shenouda and Happey (S. G. Shenouda and F. Happey, European Polymer Journal 12 (1975) 289) or Saxena, et al. (V. P Saxena, et al., Journal of Applied Polymer Science 7 (1963) 181). Ethylenediamene-water solutions are chilled to 0° C. followed by stirring in zinc oxide powder. Continuous stirring for 72 hours while maintaining the temperature at 0° C. produces a suitable Zincoxen solution. Pulping conditions using a Zincoxen pulping reagent are generally basic and may be carried out at pH above 12, or above 13, or at a pH of about 14 in a closed reaction vessel.
- In general, residence times of up to 4-48 hours in the pulping stage are suitable to dissolve and promote molecular separation of cellulose molecules present in the treated cellulose-containing feedstock. In some embodiments, the pulping stage takes place in a closed chamber and an inert gas, such as nitrogen or argon, is introduced in the airspace to inhibit or prevent oxidation of pulping solution constituents. Oxygen-containing gases may be substantially evacuated from the pulping stage. In some embodiments, agitation of the pulping mixture, mixing of the pulping mixture, or both, may be provided; in some embodiments, an inert gas, such as nitrogen or argon, may be bubbled through the pulping mixture prior to pulping, during pulping, or both.
- The cellulose molecules are substantially isolated and may be fully or partially dissolved to form substantially linear cellulose chains in the pulping stage, depending on the reagent used and the residence time. The pulping solution is filtered, following a suitable residence time, to remove non-cellulosic constituents with the solution and isolate substantially purified cellulose polymers, which are typically suspended in a viscous media. Filtration may involve multiple stages, including an optional centrifugation stage and one or more size exclusion filtration stages. A final filtration stage using pore sizes of 1 micron or less may be employed. The isolated, substantially purified cellulose polymers may be used in a wide range of downstream applications (See, e.g.,
FIG. 1 ) and, in particular applications, are used in fiber production applications to produce regenerated cellulosic fiber (See, e.g.,FIGS. 2-7 ). - The conditions of the pulping stage and the composition of the fabric feedstock are important factors in determining whether a cotton-like fiber or rayon is produced form the pulped cellulosic materials in subsequent processing. Full dissolution of the cellulosic fibers is generally desirable for the production of rayon-like fibers, cotton-like fibers and other regenerated cellulosic fibers. Suitable solvent concentrations, reagent to feedstock ratios, residence times, and the like, may be determined using routine experimentation. While Schwiezer's Reagent and the other iron- and zinc-containing pulping reagents described above are suitable pulping solvents for many applications, it will be appreciated that other pulping reagents may be available, or may be developed, and would be suitable for use in the processes described herein.
- In some embodiments, energy is introduced to the pulped solution during a desired degree of pulping, following a desired degree of pulping, or both. When the pulping stage is carried out in a closed reaction chamber, mechanical energy, electrical energy, such as radio frequency energy, or both, may be introduced during or following pulping to enhance separation of different components and promote sedimentation of heavier components. If the cellulose-containing feedstock was not pretreated to remove non-cellulosic components, suitable filtration, screening exclusion treatment, size exclusion treatment, the like, or combinations or multiples thereof, may be performed, during or following pulping, to remove non-organic materials (e.g., buttons, fasteners, zippers, etc.), as well as impurities and non-cellulosic materials from the fiber pulp solution. Suitable f filtration, screening exclusion treatment, size exclusion treatment, the like, or combinations or multiples thereof, will depend on the types and level of contaminants remaining in the fiber pulp solution. Filtration may involve scraping the top of the reaction vessel, the bottom of the reaction vessel, or both, to remove floating or sinking debris; simple size exclusion filtration; gravitation separation or centrifugation to separate solids from the dissolved cellulosic materials; the like, or combinations or multiples thereof. In some embodiments, a cascade of progressively smaller pore size filtration stages may follow preliminary separation by gravitation or centrifugation.
- Separated by-products may be isolated and purified (if appropriate) for re-sale or distribution to secondary markets.
- In some embodiments, the pulping solution may be optionally treated with glycerin or glycerol or another agent to impart softness to the texture of the fiber.
- After pulping, isolated cellulose molecules may be extruded to form regenerated fibers and textile materials. The isolated cellulose molecules are generally filtered or otherwise separated, and may be acidified and processed in a wet extrusion stage to precipitate cellulose fibers and produce cotton fibers, rayon fibers, or a mixture of cotton and rayon fibers. Various acids may be used in this precipitation stage, such as sulfuric, citric or lactic acids. In one embodiment, a sulfuric acid bath is used in combination with a wet extrusion process, wherein the viscous cellulose polymer solution is pumped through a spinneret, and the cellulose is precipitated to form fibers as it contacts the acid bath. The extrusion process, system, or both, may be modified and adjusted to produce fibers having different lengths, diameters, cross-sectional configurations, durability, softness, moisture wicking properties, and the like. In this process, the newly formed fibers are stretched, blown, or both, to produce desired configurations, washed, dried, and cut to the desired length.
- Closed vat, continuous fiber extrusion techniques may be used. Closed vat systems allow recovery, recycling, or both, of any produced gases and by-products. Using fiber extrusion techniques is highly advantageous when applied to the regeneration of cellulosic materials to produce cotton fibers, rayon fibers, or both, since it allows a high degree of custom design and engineering of cellulosic fibers to achieve targeted comfort and performance characteristics (e.g., fiber length, diameter, cross-sectional shape, durability, softness, moisture wicking, etc.). Naturally grown fibers cannot be produced in desired or specified fiber lengths, diameters, cross-sectional profiles, or the like and cellulosic fibers regenerated using this process may therefore have different, and superior, properties compared to the natural fibers present in the initial recycled fabric feedstock.
- In some embodiments, fiber extrusion may produce fibers having a denier of from about 0.1 to 70 or more denier. In some embodiments, fiber extrusion may involve extruding multifilaments having from about 20 to 300 single monofilaments, each having a denier of from about 0.1 to about 2. Extruding fine denier filaments produces woven fabric that feels softer to the touch and is desired in many embodiments. In some embodiments, fiber extrusion may additionally involve adding a false twist to the extruded filaments and texturizing them to resemble spun yarn. These treatments may obviate the necessity of using opening and spinning processes to produce yarn from the extruded fibers. Further handling of the fibers may involve cutting the continuous fiber to specific uniform lengths (stapling), missing, opening, carding, drawing, rowing, spinning, etc.
- Following fiber extrusion and spinning to form yarns, fabrics, textiles and the like, waterless dyeing techniques may be used to further reduce the environmental impact of the overall process. Waterless dyeing technologies are available and typically use supercritical carbon dioxide as a solvent and carrier for dyestuff. In some embodiments, color treatment of regenerated fibers may involve determining the absorbency of the regenerated fiber and determining the color properties of fibers using spectrophotometric techniques. Color signatures and dye formulations may then be customized according to the specific properties of regenerated fibers to eliminate differences in coloration that may result from different batch qualities. In some embodiments, regenerated fibers or yarns may be surface treated (e.g., using a bleaching composition) and then dyed or overprinted using, for example, reactive, direct, pigment, sulfur, vat dye types and prints, the like, or combinations or multiples thereof. In some applications, all fiber regeneration process steps, from garment reclamation to fiber extrusion, may be located at a common geographic site (or at nearby sites). For some purposes, it may be desirable to locate different stages of the process at different physical locations. It may be desirable, in some applications, for example, to locate garment reclamation sites in populous areas, while locating other processing facilities and, in particular, the wet extrusion facility, in locations proximate textile processing facilities—e.g. near textile mills, garment manufacturing facilities, the like, or combinations or multiples thereof. In some applications, garment reclamation and initial processing may take place at one location and cellulosic pulp may then be shipped or transported to a different location for wet extrusion and other downstream processing (e.g., dying, garment manufacturing, etc.).
- Regenerated cellulosic fibers (e.g., cotton, rayon, or both) produced as described above may be twisted into thread, dyed, bleached, woven into textiles and, ultimately, cut and sewn into garments.
- In another aspect, fiber pulping of low grade cotton fibers, harvested naturally or produced from a raw material fabric feedstock as described above, is provided. In this process, low grade natural cotton fibers (e.g., low staple length cotton fibers) may be pulped as described herein, and then acidified and subjected to a wet extrusion process to produce newly formed fibers which may be stretched, blown, or both, to a desired diameter, cross-sectional profile or the like, washed, dried, and cut to a desired length. In this fashion, low grade (natural, recycled, or both) cotton fibers may be regenerated and converted to newly formed, higher value fibers having more desirable properties than those of the original natural cotton fibers, recycled cotton fibers, or both.
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FIG. 8 shows a schematic flow diagram illustrating the processing of a blended textile input according to methods described herein. In this scenario, blended textile input is separated into cotton-heavy and polyester-heavy blends during one or more sorting and pretreatment step(s). The constituent cotton and polyester polymers in each of the separated stages are dissolved and isolated to produce “liquefied” cellulose (from the cotton-heavy feedstock) and “liquefied” polyester from the polyester-heavy feedstock. These isolated cellulosic and polyester materials may be extruded into regenerated fibers, as desired, or used for other downstream applications. The undissolved, non-cellulosic constituents remaining after dissolution of the cotton-heavy blend feedstock may be treated for dissolution of polyester to produce liquefied polyester. Likewise, the undissolved, non-polyester constituents remaining after dissolution of the polyester-heavy blend feedstock may be treated for dissolution of cellulose to produce a liquefied cellulose. Undissolved components such as other fibers, zippers, buttons, and the like, may be collected and re-used or discarded. - Although the process has been described primarily with reference to using cotton garments and feedstock containing cotton materials, it will be appreciated that other types of fabrics may be pulped and regenerated using the same or similar processes to produce regenerated fibers. It will also be appreciated that additional process steps may be employed, as is known in the art, and that equivalent treatment steps may be substituted for those described above.
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FIG. 10 shows a schematic flow diagram outlining process steps as disclosed herein for producing paper or packaging materials from a combination pulp including a textile pulp and a wood pulp. After pulping, a textile pulp (i.e., pulp made or derived from textiles, as discussed above, which includes cellulosic material and can also include non-cellulosic material) can be mixed with wood pulp to form a combination pulp used to develop packaging material (e.g., cardboard boxes, corrugated cardboard, cardboard liner, or components of a cardboard box), paper products (e.g., toilet paper, paper towels, wet wipes, printer paper, or the like), or the like. Therefore, recycled textiles can be used to obtain a first pulp which is mixed with a second pulp derived from a wood pulping process. - Wood pulp includes three components: cellulose, hemicellulose, and lignin. The percentage of the components can be affected by type of wood (e.g., hard vs. soft), climate (e.g., temperate), the like, or combinations thereof. Cellulose maintains the strength in wood fiber due, at least in part, to the high degree of polymerization and linear orientation of the cellulose. Hemicellulose acts as the matrix. Lignin acts as the glue, thereby holding the fibers together and the cellulose together within the fiber cell wall. The wood can be processed to obtain pulp having a cellulose content based on the subsequent use. Wood pulp can be formed by any appropriate process or system, including, for example, mechanically, chemically, thermochemically, chemi-thermochemically, the like, or combinations or multiples thereof.
- For example, a first wood pulp having the highest cellulose content (e.g, >90%) can be used to form textile fibers, derivatized celluloses, cellulose ethers, or the like. As another example, a second wood pulp having an intermediate cellulose content (e.g., 20-45%) can be used to form paper products. As yet another example, a third wood pulp having the lowest cellulose content (e.g, <10%) can be used to form cardboard.
- Before textile pulping, during textile pulping, or after textile pulping, the textiles can undergo additional processing to change a size characteristic or parameter of a textile fiber or cellulose fiber derived from processing the textile. The textiles, whether as a pulp or otherwise, can be processed with a Tornado pulper, a refiner, a valley beater, the like, or combinations or multiples thereof. The size characteristic or parameter of the textile fiber or cellulose fiber derived from processing the textile can be the same as or substantially the same as (i.e., ±20%) as a size characteristic or parameter of the wood pulp fibers (e.g., average size of textile fiber or cellulose fiber is within a 20% difference of an average size of fibers of the wood pulp). The size characteristic or parameter of the textile fiber or cellulose fiber derived from processing the textile can be reduced to prevent a paper or cardboard production machine from jamming, malfunctioning, or the like due to the excessive size of the textile fiber or cellulose fiber derived from processing. For example, a textile fiber or cellulose fiber derived from processing the textile can have a length of 4-8 millimeters (mm). The length of the textile fiber or cellulose fiber can be reduced to, for example, 0.5 to 4 mm by undergoing the additional processing. As another example, a textile fiber or cellulose fiber derived from processing the textile can have a weight of 2.2-2.5 Deniers per filament (Dpf). The weight of the textile fiber or cellulose fiber can be reduced to, for example, 0.5 to 1 Dpf by undergoing the additional processing.
- The textile pulp and the wood pulp can be mixed by any appropriate process or system, including, for example, two pipes flowing into a single pipe, adding the different pulps to a single vessel for blending, the like, or combinations or multiples thereof. Mixing the textile pulp with the wood pulp can increase yield by combining a lower cellulose content pulp (i.e., wood pulp) with a higher cellulose content pulp (i.e., textile pulp). Additionally, typically discarded wood pulp components, such as lignin, can be retained in wood pulp, thereby reducing cost, increasing yield, or the like. For example, during the wood pulping process, lignin can be burned off with the resulting steam used to generate energy. In doing so, the volume of the pulp is reduced and an additional step is required. However, retaining the lignin increases the mechanical stress (e.g., compression, tension, shear, bending, torsion, fatigue, the like, or combinations of multiples thereof) capability of the resulting product, whether paper, cardboard, or the like.
- Based on the respective cellulose content of the textile pulp and the wood pulp, the amount of textile pulp and the amount of wood pulp can be adjusted to form a combination pulp having the desired cellulose content. The ratio, as a percentage, of textile pulp and wood pulp in the combination pulp can range from 0.1:99.9 up to at least 55:45, including, for example 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, and the like. For example, 150 kg of a wood pulp having 4% cellulose can be combined with 8 kg of a textile pulp having 90% cellulose to form a combination pulp having a cellulose content of 8.35%, such as for developing cardboard. As another example, 150 kg of a wood pulp having 15% cellulose can be combined with 120 kg of a textile pulp having 75% cellulose to form a combination pulp having a cellulose content of 41.67%, such as for forming paper products.
- The textile pulp can also include non-cellulose material, such as a polyester, nylon, rayon (or Lyocell), acrylic, the like or combinations or multiples thereof. The non-cellulose material can increase the mechanical stress (e.g., compression, tension, shear, bending, torsion, fatigue, the like, or combinations of multiples thereof) of the resulting product, e.g., paper product or cardboard. Additionally, or alternatively, non-cellulose material can be added to the textile pulp, the wood pulp, the combination pulp, or combinations thereof to increase the mechanical stress of the resulting product.
- The processing steps used to form the textile pulp, the textiles, fibers, or derivatives thereof can be adjusted based on the resulting product to be developed. For example, when the textile pulp is used to develop paper products, a bleaching step (e.g., bleach intensity, number of bleaching steps or sub-steps, or the like) can adjust the color of the fibers. As another example, when the textile pulp is used to develop cardboard, a sorting step can be less thorough (e.g., instead of separating recycled textiles in bins based on increments of 2-3% cellulose content, the recycled textiles can be separated into bins based on increments of 10-15% cellulose content).
- Though textile pulp is discussed in reference to the combination pulp, the textile pulp can be further processed by one or more dissolving steps, as discussed above, before forming the combination pulp, when it is necessary or desirous to do so.
- A small scale experiment was conducted to establish feasibility of cellulose pulping and fiber regeneration using shredded cotton garment material as a feedstock. The shredded feedstock material was treated with Schweizer's Reagent to form a dissolved pulping solution, and the pulp solution was acidified by treatment with sulfuric acid. Fibers were regenerated as a result of the acidification.
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2 NaOH(aq)+CuSO4(aq)→Cu(OH)2(s)+Na2SO4(aq) 1. -
Cu(OH)2(aq)→Cu2(aq)+2OH−(aq) 2. -
n Cu2+(aq)+(cellulose)n+2n OH−→(CuC6H8O5)n+2n H2O 3. -
- 4. Cellulose is actually dissolved in [Cu(NH3) 4](0 H)2 solution and then regenerated as cotton or rayon when extruded into sulfuric acid.
- 5. Note: Filtration of Cu(OH)2 can be a problem; small amounts of precipitate should be filtered and then combined in one container.
-
-
- 1. Dissolve 25.0 g of CuSO4.5H2O in 100 mL distilled water. Heat the water to accelerate the dissolving process.
- 2. Dissolve 8.0 grams NaOH in 200 mL distilled water.
- 3. Mix the cooled NaOH solution with the copper sulfate solution. Collect the resultant gelatinous precipitate of Cu(OH)2 by filtration. Wash the precipitate with three 10-mL portions of distilled water. If using 11.0 cm filter paper, several filtrations will be required because of the large amount of precipitate produced.
- 4. Measure 70 ml concentrated NH3(aq) into a 250-mL Erlenmeyer flask. Shred 10-15 grams cotton garment. Add the Cu(OH)2 precipitate carefully along with the filter paper to this flask and stir. This should result in a deep purplish-blue solution of tetra-aminecopper(II) hydroxide, referred to as Schweizer's reagent. Stopper the flask and stir periodically for 24 hours or more. Use a magnetic stirrer, if available. One may dip the flask in warm water to speed the process.
- 5. Take up the contents of the 250-mL Erlenmeyer flask in 10-mL increments in a 10-mL or 50-mL syringe. Squeeze out the contents into a 1000-mL beaker containing 300 mL of 1.6 M sulfuric acid. Be sure that the tip of the syringe or pipet is under the surface of the acid. Crude “thread” forms.
- 6. The clumps or threads can be washed free of the solution to show the blue-cast white color of the regenerated fibers. Subsequent analysis will demonstrate whether the regenerated fibers have the structure of cotton or rayon.
- In alternative schemes, chemical reaction (1), noted above, may be omitted when using copper hydroxide and ammonia reactants to form Schweitzer's reagent as follows: Cu(OH)2+4NH3+2H2O→[Cu(NH3)4(H2O)2]2++2OH This alternative chemistry does not require filtration (setp 5, above) and produces no by-products that require disposal or removal.
- Analyses were conducted to compare regenerated cellulosic fibers, processed as described herein, with virgin cotton fibers. Regenerated cellulosic fiber produced as described above was tested using the ASTM D 2256-02 test method for tensile properties of yams by single-strand method. The regenerated cellulosic fibers exhibited uniform-diameter fiber properties, with the tenacity of cotton and the fineness of silk. Tenacity is a measure of the breaking strength of a fiber divided by the denier.
FIG. 9A shows a magnified image of a regenerated cellulosic fiber produced as described above (on the left, labeled Evmu) andFIG. 9B shows a magnified image of a premium long-staple cotton fiber as tested in Harzallah, Benzina & Drean, 2009 (right-side image, labelled “cotton,” reproduced without permission from aforementioned paper). The comparative fiber properties of the regenerated cellulosic fiber produced as described above and the premium long-staple cotton fiber, as reported in the above-mentioned literature reference, are outlined below. -
Fiber properties EVRNU Comparison Cotton Fiber diameter in micrometers 20 to 100 226.2/80.3 (mean/standard deviation) (can be customized) Tenacity (gf/tex)-mean 21.96 21.01 Tenacity (gf/tex)-standard 0.64 0.61 deviation Elongation %--mean 2 to 4% 8.4% (depends on crystallinity) Sample Size & Comments Sample size Cotton #1 sample, of 3 fibers tested via the MVI method, is selected from Harzallah, Benzina & Dean 2009. Sample size of 25 fibers.
The tenacity tests indicate that regenerated cellulosic fiber produced as described above has similar strength to the tested cotton, for its diameter. Extrusion allows the diameter (and hence absolute strength of individual fibers) to be tightly controlled. -
FIG. 9C shows a magnified cross-sectional image of a regenerated cellulosic fiber produced as described above. Extrusion allows for precision control and consistency in fiber cross-section and length. Regenerated cellulosic fibers produced as described herein may be extruded under various conditions and to produce different fiber cross-sectional profiles and lengths. In general, regenerated cellulosic fibers produced herein may be extruded just as other manmade fibers and can be prepared as mono, multifilament or stapled in desired length for ring/OE spinning. - Though certain elements, aspects, components or the like are described in relation to one embodiment or example of a system or method for producing a paper or packaging material, those elements, aspects, components or the like can be including with any system or method for producing a paper or packaging material, such as when it desirous or advantageous to do so.
- The foregoing description, for purposes of explanation, used specific nomenclature to provide a thorough understanding of the disclosure. However, it will be apparent to one skilled in the art that the specific details are not required in order to practice the systems and methods described herein. The foregoing descriptions of specific embodiments or examples are presented by way of examples for purposes of illustration and description. They are not intended to be exhaustive of or to limit this disclosure to the precise forms described. Many modifications and variations are possible in view of the above teachings. The embodiments or examples are shown and described in order to best explain the principles of this disclosure and practical applications, to thereby enable others skilled in the art to best utilize this disclosure and various embodiments or examples with various modifications as are suited to the particular use contemplated. It is intended that the scope of this disclosure be defined by the following claims and their equivalents.
Claims (19)
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CN115093616A (en) * | 2022-06-11 | 2022-09-23 | 云南杰商科技有限公司 | Environment-friendly composite carton made of konjac mannan and preparation method of environment-friendly composite carton |
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