CN112981578A - Post-treatment and finishing process - Google Patents
Post-treatment and finishing process Download PDFInfo
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- CN112981578A CN112981578A CN201911273849.5A CN201911273849A CN112981578A CN 112981578 A CN112981578 A CN 112981578A CN 201911273849 A CN201911273849 A CN 201911273849A CN 112981578 A CN112981578 A CN 112981578A
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- bath
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- fluff
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- 238000009987 spinning Methods 0.000 claims description 61
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 20
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- 239000013589 supplement Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 55
- 229920000297 Rayon Polymers 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 27
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- 239000007789 gas Substances 0.000 description 17
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- 229910052725 zinc Inorganic materials 0.000 description 12
- 230000032683 aging Effects 0.000 description 9
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- 238000011069 regeneration method Methods 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
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- 239000012535 impurity Substances 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
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- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 101710178035 Chorismate synthase 2 Proteins 0.000 description 3
- 101710152694 Cysteine synthase 2 Proteins 0.000 description 3
- 206010016807 Fluid retention Diseases 0.000 description 3
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- 239000007832 Na2SO4 Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 239000002699 waste material Substances 0.000 description 3
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- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000011956 best available technology Methods 0.000 description 2
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- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- USAIOOFEIMNEDN-UHFFFAOYSA-L disodium;carbonotrithioate Chemical compound [Na+].[Na+].[S-]C([S-])=S USAIOOFEIMNEDN-UHFFFAOYSA-L 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B9/00—Cellulose xanthate; Viscose
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention relates to a method for post-treatment and finishing. In particular, the invention relates to a process for producing modal fibers, wherein the finishing step in the post-treatment consists at least of a final wash zone, a first extrusion device, a soft finishing bath and a second extrusion device, wherein the finishing step is operated in such a way that the intake of liquid into the soft finishing bath after the first extrusion device is less than the output after the second extrusion device.
Description
Technical Field
The present invention relates to a modal process.
The modal fibers are characterized by the minimum requirements for tenacity and wet modulus according to the definition of BISFA. In addition, the technology used to make modal fibers with their unique combination of physical and textile properties, softness and fabric stability should meet the IPPC guidelines of the european ecolabel and Best Available Technology (BAT) for emissions from processes produced by proprietary manufacturing methods.
Background
Compared to the conventional viscose process, the key element of the process is a balanced combination of the following factors: low hemicellulose concentration in the impregnation lye, short ageing time and higher DP of the cellulose, higher input of carbon disulphide (CS 2) and sodium hydroxide (NaOH), use of special modifiers, viscose fibres with low cellulose concentration, high alkali ratio and high viscosity, lower concentrations of sulphuric acid and sodium sulphate and high zinc concentration in the spinning bath, higher number of spinneret holes, high drawing and low spinning speed and high specific formation and yield of sodium sulphate. In particular, the method may consist of the following method steps:
slurry material
All dissolving grade slurries of sufficient purity, reactivity, whiteness and appropriate viscosity are useful in the modal process. Such pulp can be prepared from softwood or hardwood or even non-wood materials by sulfite or sulfate techniques and used in the form of sheets, rolls or flakes. The integrated preparation of pulp and fibers allows the use of wet pulp, which can be fed directly into the pulper without the need for drying. The subsequent process steps in viscose manufacture need to be adjusted due to the physical and chemical performance of the pulp. The slurry may also contain an impregnation aid, which is a surfactant for better penetration of the impregnation lye.
Pulping
Wood-based cellulose, such as baled dry or wet pulp (48-50% dry matter), is mixed with a temperature-controlled sodium hydroxide liquor (impregnation liquor) containing 220-240g/l total alkali in a number of pulpers equipped with special turbine stirrers. Alkali Cellulose (AC) is formed from the reaction of cellulose with sodium hydroxide. Impurities like so-called "hemicellulose" and its degradation products are dissolved in the liquid.
The slurry is stored in a slurry tank from which it is continuously pumped to an AC press which separates the alkali cellulose from the pressed alkali liquor.
Alkali Cellulose (AC)
After pressing the pulp in a drum or belt press, a wet cake of alkali cellulose containing 32-34% cellulose and 15-17% caustic soda is obtained. The AC is crushed to obtain a high specific surface area prior to the aging process.
AC aging (Pre-aging)
The aging process is necessary to adjust the degree of polymerization of cellulose by depolymerization in the presence of air or oxygen in order to obtain the desired viscosity of the spinning solution. The shredded alkali cellulose is aged in a belt aging, aging drum, tower or cabinet apparatus. The aging time can be adjusted by varying the speed and temperature of the conveyor or drum, depending on different requirements. If desired, the pre-maturation process may be accelerated by adding a catalyst, such as cobalt chloride or manganese sulphate, to obtain an AC (SCAN) having an intrinsic viscosity of 400-450 ml/g.
After aging, the alkali cellulose is cooled in an alkali cellulose cooler, which operates as a fluidized bed reactor. A rotary cooling drum or a continuous flow conveyor may also be used.
Xanthation
The alkali cellulose is reacted with CS2 to give sodium xanthate, which is soluble in dilute sodium hydroxide (dissolving lye). For this purpose, AC was fed into the xanthator through a conveyor belt and a weigh bin. The exothermic reaction of AC with carbon disulphide is controlled by cooling the AC.
The reactor used may be a wet churn equipped with an intensive kneader, a continuous twin-screw kneader or a belt xanthator. Under vacuum, AC was reacted with CS2 liquid and kneaded like a dough until the reaction was complete. The CS2 input may be 35-38% based on cellulose.
CS2 also reacts with NaOH as a by-product of xanthate formation to form Na2CS3 and Na 2S.
A sufficient degree of substitution is required to dissolve the xanthate in dilute NaOH, expressed as ɣ value (CS 2 moles per 100 moles of glucose units). The concentration of sodium hydroxide determines the alkali content of the viscose. By varying the degree of substitution, the alkali-/cellulose ratio and the average length of the chains, viscose fibers of different quality can be achieved.
The xanthation apparatus may be of the Simplex or Suma type. The temperature at the beginning of the xanthation may be between 15 and 17 ℃ and the temperature at the end of the xanthation between 30 and 35 ℃.
Dissolution
The mixture of lye and xanthate is discharged into the dissolver through the homogenizer by feeding the cooled dissolved lye into the xanthator.
Homogenization of viscose fibres is achieved in a fine homogenizer at low temperature. The modifier is added to the viscose dope. The function of the modifier is to control coagulation and regeneration during filament formation in the spinning process. Many different compounds or their blends can be used as modifiers: amines and polyamines, quaternary ammonium compounds, amides, heterocyclic nitrogen compounds, polyglycols, ethoxylated ammonia derivatives, ethoxylated fatty acid amines and amides, ethoxylated glycerol and ethoxylated fatty acids, esters or alcohols. Many examples of these compounds, which may be used alone or as blends, are described in the k. foster ribbon tze, "Chemiefasern nach dem viskosher fahren", third edition, Springer, 1967, pp 635-641, the disclosure of which is incorporated herein by reference.
The amount of modifier is 1.0-4.0% based on cellulose.
The modifier can be added during the dissolution process, preferably directly into the dissolver, after degassing before the final filtration of the viscose fibers or directly before spinning.
This can be done by means of generally known devices for introducing substances into a stream of liquid medium. Preferably, there is a means, such as a static or dynamic mixer, after the addition location to provide uniform distribution of the modifier within the viscose fibers. Such mixers are well known and commercially available, for example Sulzer mixers. In a continuous process, the viscose fibres from the dissolver are further treated in two refiners to improve the dissolution state.
The unfiltered viscose fibres may have a cellulose content of 6.0-7.0%, an alkali content of 6.0-7.0% and a sulphur content of 1.7-2.0%.
Aging, filtering and degassing
After homogenization of the xanthate, the viscose fiber must go through successive maturation, degassing and filtration processes.
The ripening is carried out in tanks in order to obtain a better distribution of the xanthate groups on the cellulose chains and to obtain the desired ripening index or gamma value for the subsequent spinning process.
Prior to spinning, viscose fibres must be filtered to remove fibres, gel particles or other impurities, as this can block the fine spinneret holes and cause spinning defects. Instead of a conventional filter press, a continuous waste filter can be used, which is equipped with fine metal fiber fluff of different pore sizes. The filtration process is carried out in two or three steps in order to obtain the best filtrate quality.
Continuous rapid degassing to remove air bubbles was performed before pumping the viscose fibers to the spinning tank.
The spun viscose fibres may have a ball drop viscosity of 80-140s, a gamma value of 57-64, a cellulose content of 6.0-7.0%, an alkali content of 6.0-7.0%, a sulphur content of 1.6-1.9% and an alkali/cellulose ratio of 0.95-1.1.
Spinning
The modal staple fibers were produced on a spinning machine consisting of a spinning tank containing a spinning bath, a rotating godet with a variable drive and a ceramic guide for taking up the filaments and a final draw roll for collecting the individual tows after drawing in a hot secondary bath. Such draw rolls may be, for example, a triad of two sets of pressure rolls that squeeze the tow and reduce chemical entrainment into the acid wash, or a series of six or more non-squeeze rolls.
Viscose fibers were pumped by a gear pump, passed through a candle filter, and extruded through the fine holes of a spinneret immersed in a spinning tank.
Different spinning geometries can be applied for modal fibers: diagonal or vertical spinning, where there are two or three tows per godet.
For the purpose of ventilation, the machine is completely enclosed to recover the sulphide gases and to achieve safe working conditions in the spinning zone.
Fresh spin bath enters the spin tank from the bottom and overflows back to the spin bath system where it is degassed, filtered, excess water is evaporated, excess sulphate is crystallised and make-up chemicals are added to adjust the composition before it is recycled back to the spinning machine.
Coagulation and regeneration occur in parallel after the viscose fibres have been extruded through the spinneret holes. The viscose fibres coagulate and the high viscosity gel becomes a sol. During regeneration, xanthate is decomposed by the acid of the spinning bath into regenerated cellulose, and the caustic soda of the viscose is neutralized by the acid to form sodium sulfate. Both processes are affected by the following factors: the composition and temperature of the viscose and spinning bath, the type and concentration of the modifiers (which delay the regeneration process and their interaction with the components of the spinning bath), the spinning speed, the spinning geometry and the immersion length of the filaments, the spinning bath/viscose flow rate and the diameter and design of the spinneret holes, and therefore a careful balance is required to obtain fibers with the required physical parameters without spinning defects.
The tow from two or three spinnerets was collected, guided by a ceramic guide and wound three times around a godet roll. The tow is drawn by a take-up roll at the end of the spinning machine, the tow is introduced into a hot secondary bath (drawing bath) where the regeneration is completed and high drawing is applied so that the filaments gain strength by fixing the oriented cellulose molecules.
Due to the delayed regeneration, the spinning speed in the modal fiber process is much lower than in the conventional viscose process and can be 25 to 40m/min and higher elongations to 125% can be applied.
Spinning nozzle
Spinneret design and spinning geometry are key factors in achieving high quality modal fibers at high line efficiencies. Modal fibers need to be spun at much lower spinning speeds than viscose fibers, which can be compensated for by spinnerets with significantly higher hole counts. Such cluster spinnerets consist of cups arranged on a plate, which may be a full disc or an annular plate. The cup may be 12 to 16mm in diameter, with the hole diameter depending on the fibre titer (titer). The total number of holes per spinneret can be as high as 100,000 or even higher. In order to achieve a sufficient immersion length, the filaments are spun vertically or diagonally at an angle. The immersion length may be 40 to 80 cm.
Spinning bath
The spinning bath is an aqueous solution of sulfuric acid, zinc sulfate and sodium sulfate, which is circulated through the spinning machine. The viscose fibres are coagulated by the salts present in the bath and decomposed by the acid, giving regenerated cellulose filaments, Na2SO4, CS2 and H2S. In the spin bath circulation system, excess Na2SO4 is removed by crystallization, the sulfide gas is collected and recovered as CS2, sulfur or converted to sulfuric acid, and make-up chemicals sulfuric acid and zinc sulfate are added to adjust the spin bath composition.
In the spinning bath, the H2SO4 concentration may be 70-90g/l, the Na2SO4 concentration 90-130g/l, the ZnSO4 concentration 48-62g/l, and the temperature 37-43 ℃. The spinning speed, spinneret size, modifier type and spin bath composition (including temperature and dip length) are not independent of each other, but need to be well balanced to achieve the desired fiber properties.
Stretching bath
The drawing bath is an encapsulated hot acid bath comprising the spinning bath components in diluted form at a temperature of 90 to 98 ℃. Its function is to apply maximum tow draw between the godet and draw units while the regeneration process is still in progress to wash the tow to reduce spinning bath chemical carryover into post-processing and to collect sulfide gas from the system for recovery.
Cutting of
The tow from all godets was collected on a drawing unit to obtain a thick wire which was sucked into the wire injector of a cutter with acidic water and cut to the desired staple length with a rotating self-sharpening cutter.
The cut staple fibers were then washed with acidic water into the CS2 tank of the washing track for post-treatment.
As an alternative to injection wet cutters, dry cutters are used, which are horizontal discs with fixed knives. The cable is wrapped around the disc and cut by pressing the second disc towards the knife.
Post-treatment
The different stages of the process are fluff formation, treatment with acidic water, desulphurization, bleaching, washing and finishing (refining). The process is carried out on an enclosed washing track, which may be a belt or an eccentric conveyor, which conveys the fiber fluff through the aftertreatment, during which it is rinsed with different liquids. The press rollers between the washing zones reduce the entrainment of chemicals.
The staple from the cutter was washed into a CS2 tank and treated with hot acidic water. When the residual CS2 is released and subsequently recovered from the exhaust gas, the short fibers open and form fluff, which is picked up by the scrubbing track. The uniformity of the fluff is critical for uniform fiber quality.
In the first zone, residual sulfide compounds are removed by treatment with hot acidic water. After pressing, the fluff was washed with soft water in a counter-current. Fresh water is added before finishing and reused for washing after bleaching, after desulphurization and after acid treatment.
Desulfurization is carried out by treatment with a dilute caustic soda and sodium sulfide mixture to dissolve and remove sulfur residues.
Sodium hypochlorite is used as a bleaching chemical.
Before the final finishing step, the fluff is washed with soft water and dewatered with high-pressure rollers in order to reduce the liquid intake (intake) into the finishing zone to and achieve maximum finishing absorption.
Finishing is an important process for preparing the surface of fibers for further processing in yarn spinning or non-woven processes. The different components are mixed to obtain an optimal balance between adhesion, slip and antistatic properties.
After finishing, the fluff was dewatered with a high pressure roller to minimize the water content before drying. Compact wet fiber mats require a wet opening process that is performed in two or three stages using spiked rollers of different strengths to prevent fiber damage. The wet opened fibrous fluff can now be dried.
Drying, opening and packaging
Drying can be carried out in a belt dryer or drum dryer with hot air in countercurrent. The screen drum dryer consists of a series of rotating drums, each of which contains a wire jacket and a fan. Hot air is drawn into the drum interior through the fluff, which dries and presses the fluff onto the wire sleeve. By blocking half of the drum cylinder, fluff is transferred to the next drum and turned over. After passing through the first zone of the dryer, the fluff is opened again to obtain a uniform moisture profile and rearranged for the final dryer zone. At the end of the drying process, the fibers are rewetted to adjust the fiber moisture to the desired level. After drying has been completed, the final opening process is carried out in one or two stages to produce a uniform and large quantity of product ready for packaging.
Spinning bath degassing and filtration
During spinning, CS2 and H2S dissolved in the spinning bath and needed to be removed by degassing. By spraying the spinning bath in a degasser under vacuum, the gas is released and used as rich gas to produce sulfuric acid.
After filtering the degassed spinning bath through sand or candle filters, the composition of the spinning bath is adjusted by the dosage of sulfuric acid and zinc sulfate and returned to the bottom tank of the spinning bath cycle.
Evaporation of
During spinning, the spinning bath is diluted by the water taken in from the viscose and the water formed by neutralization of NaOH with sulfuric acid. In order to maintain the desired spin bath concentration, excess water must be removed by a thermal multistage evaporation device. The high efficiency flash evaporator operates at low specific steam consumption.
Crystallization of
In the modal process with a high base ratio, the amount of sodium sulfate formed by the neutralization reaction is significant. The process by-products must be removed and recovered from the spinning bath.
This is accomplished by a crystallizer that uses caustic soda or sulfuric acid as a vapor absorption method to cool the temperature of the spinning bath. Crystals of mirabilite (Na 2SO4 x 10H 2O) were grown in large drums and separated by propeller centrifuges.
Calcination of
In order to make sodium sulfate transportable and usable, the crystal water of mirabilite needs to be removed. For this purpose, pressure calcination is used. After melting the salt cake, the melt was directed through a calcination evaporator. The crystals were thickened by a second set of centrifuges and then separated. The anhydrous sodium sulfate is dried, stored and packaged.
Recovery of CS2 by condensation
Water vapor, a mixture of CS2 and H2S, was drawn from the fluff forming unit. Most of the vapor is condensed and returned to the CS2 tank. The remaining gas passes through the condenser and is sucked out by the water jet, wherein CS2 is condensed by cold water. The separator after the water jet separates the process water and condensed CS2 from the uncondensed gases. The uncondensed gases are drawn off to an exhaust system for further processing to sulfuric acid. The liquid CS2 is separated in the settler and recycled to the viscose process without any additional cleaning.
Recovery of CS2 (CAP) by adsorption
The CS2 off-gas having a low concentration of H2S was recovered by the CAP process (carbon adsorption plant). It is a batch process with cycles of adsorption and desorption of CS2 by activated carbon. Prior to applying the adsorption process, H2S had to be removed from the feed gas with NaOH in a gas scrubber. The obtained mixture of NaOH and Na2S can be used in the desulfurization process of the fiber post-treatment. The feed gas concentration should be high but must be outside the explosion limits. The liquid CS2 from desorption can be directly recycled into the process.
WSA (Wet sulfuric acid equipment)
Among all the technologies used for treating sulfide off-gases, the WSA process is most versatile and effective in removing sulfide odor by converting CS2 and H2S into sulfuric acid, which can be used in the spinning process. By combining WSA with the condensation process, a reasonable amount of CS2 input can be recycled while achieving maximum purification efficiency. However, the economic disadvantage is that the valuable specialty chemical (CS 2) is converted into the inexpensive commodity (sulfuric acid). Depending on the exhaust gas composition, additional sulfur and fuel (natural gas, oil) are used as additional inputs and steam is produced as a byproduct.
The lean gas from spinning, the rich gas from degassing the spinning bath and sulfur were used as separate feeds for WSA. The sulfide compound is efficiently converted to sulfuric acid by the catalyst.
Zinc recovery
In the work-up, zinc is precipitated from the overflow waste water of the pickling system in the form of zinc sulphide. The zinc sulphide is separated from the slurry and dissolved with sulphuric acid to obtain again zinc sulphate, which is metered into the spinning bath for the spinning process.
Disclosure of Invention
The purpose of the fiber post-treatment process is to wash off chemicals including sulfur from the spinning process, bleach the fiber to achieve higher whiteness, and finally apply a soft finish to ensure good processability. The fibre fluff is transported on a washing track, rinsed with different liquids and pressed between the zones with a squeegee roller coated with rubber. The treatment must be uniform to obtain a homogeneous product of high purity, and the soft finish should be distributed evenly over the surface of the fibers. The final pressing of the finished fiber fluff should reduce the moisture as much as possible in order to save drying energy.
Especially in the alkaline stage of the post-treatment, the cellulose fibres swell by absorbing fluid therein and retaining fluid between the fibres. This makes it difficult for the wash liquor to penetrate the fluff and wash off the chemicals. The pH of the fiber fluff is still high due to the high pH in the alkaline treatment step of desulfurization and bleaching and the entrainment of alkali into the final wash zone. Thus, the water retention of the fluff entering the soft finish area is higher than the water retention of the fluff leaving the soft finish area.
This technique is very common in the industry and causes many problems. One problem is that the moisture from the fluff entrains liquid from one area to the next, which reduces the efficiency of the washing process. The post-treatment fluid, which is typically circulated in a closed loop system, is contaminated with spinning bath chemicals such as zinc and sulfur compounds, as well as with organic materials such as degradation products of cellulose and hemicellulose. These impurities accumulate in the post-treatment fluid and are entrained by the fiber fluff into the final soft-finish region.
In the modal fibre process, a spinning bath of high concentration of zinc is used. The zinc has a strong affinity for the cellulose and cannot be easily washed off, i.e. it is not completely removed from the modal fibre in the first post-treatment step.
In the finishing bath, the zinc impurities react with the soft-finishing soap constituents to form insoluble zinc soaps which precipitate on the surface of the fibers, with a negative effect on processability. The dissolved organic substance replaces the soft finish on the fibers. As a result, up to 30% of the ethanol extract in the fiber may consist of non-finished material, which indicates a serious quality problem. To reduce this fiber contamination, the soft finish area is operated in an open system fashion with overflow. The fluff entering the finishing bath had more moisture than after the final extrusion. Thus, the volume of the finishing bath continuously increases and remains stable by flooding. However, this leakage of contaminants through the overflow does not completely solve the quality problem, and this also results in loss of finishing chemicals and increased discharge to the waste water. Alternatively, the soft-finish area may be operated in such a way that the fluff is not pressed too much in the last press and thus enters the subsequent dryer at a higher moisture content. However, this mode of operation requires more drying energy, which is generally not preferred.
Therefore, the problem of the present invention is: a) the concentration of organic waste compounds and zinc in the soft finishing bath increases with time and causes quality problems; and b) conventional methods of solving this problem by increasing overflow result in increased emissions and waste of chemicals. The task is therefore to control the concentration of organic waste compounds and zinc in the softening finishing bath without causing increased emissions and waste of chemicals.
It has surprisingly been found that this problem can be solved by a process which reduces the entrainment of organic matter and zinc into the soft finishing bath. The principle of the invention is that the moisture content of the fiber fluff entering the soft-finish area must be lower than the moisture content after the final extrusion. By lowering the pH in the last wash zone to 5.0-6.0, a better squeezing action before entering the soft finish zone can be achieved, which reduces swelling and water retention of the modal fibers. Depending on the difference in moisture content, the circulating soft finishing bath is consumed, its volume is reduced, and impurity levels are controlled by adding pure finishing chemicals and soft water, rather than by flooding. Analysis showed that the content of non-finishing substances and zinc in the cellulosic ethanol extract was even lower than with the overflow operation. Furthermore, in the process according to the invention, the soft finishing chemicals are not wasted and do not contaminate the waste water system.
The invention presented here is particularly advantageous for the manufacture of modal fibres. However, it can also be applied in the same way to the manufacture of ordinary viscose fibres.
Since the moisture content of the fluff before finishing must be even lower than that after the final pressing, special techniques are required. Applying high pressure directly on the conveyor belt with ordinary stainless steel pressure rollers can cause damage to the belt and problems with the drive unit. In order to achieve a high dewatering of the fluff, it is therefore necessary to divide the belt and the drive system into two units and to arrange a press roll between them. With the aid of the pile guide, the pile is taken off the first belt and fed into the nip of the press rolls, where high pressure can be applied without a support belt. The second pile guide picks up the pile after pressing and transports it to a second belt where a soft finish is applied. The same technique is used in the final extrusion after finishing to achieve low moisture content before wet opening and drying.
However, the application of high pressure using conventional steel press rolls can also result in fiber damage where the fiber fluff is thick and not completely uniform. During the subsequent finishing process, these areas do not penetrate uniformly by the soft finish and remain unfinished, which can lead to quality problems.
Another more specific problem of the present invention is therefore how to obtain a high squeezing action and a uniform soft-finish distribution.
Surprisingly it has been found that this problem can be solved by using a pair of special press rolls. The bottom roller is made of stainless steel with horizontal channels and holes for better drainage of the liquid or coated with hard rubber, while the upper roller is coated with special rubber, which is much softer and more flexible than the hard steel surface. Suitable extrusion rolls are available from the company Richard Hough Ltd, Bolton, Lancashire, UK under the trade name NOLLAPTMAnd (4) obtaining. This avoids the occurrence of overpressure in the thick parts of the pile, since the rubber can adapt to the pile surface even if it is not perfectly homogeneous. In an alternative, but less advantageous embodiment of the invention, the bottom roll may also be coated with a special rubber.
The combination of such a press roll with 2 separate belt systems and the lower pH of the fiber fluff after the last washing zone can result in a fluff moisture before finishing that is even less than the moisture after the last press without negative effects on soft finish distribution and fiber quality.
The invention therefore essentially relates to a method for producing modal fibers, comprising at least the following method steps:
a. preparing alkali cellulose from a cellulose raw material,
b. the alkali cellulose is aged and the resultant is then,
c. the mixture is subjected to xanthation and acidification,
d. the mixture is dissolved and then is added with water,
e. curing, filtering, degassing,
f. the spinning bath is used for spinning the fiber,
g. stretching the mixture to obtain a stretched mixture,
h. post-treatment (including cutting, bleaching, washing, finishing, drying, opening, packaging),
i. the recovery of the chemicals is carried out by,
wherein the finishing step in the post-treatment consists of at least a final wash zone, a first extrusion device, a soft finishing bath and a second extrusion device, wherein the finishing step is operated on a separate conveyor belt in such a way that the intake of liquid into the soft finishing bath after the first extrusion device is less than the output of liquid after the second extrusion device. The first and second pressing means may be both pairs of press rolls; however, other devices suitable for squeezing out liquid from swollen cellulosic fiber fluff may be used. Preferably, the soft finishing bath operates without flooding.
In a preferred embodiment of the invention, the line pressure of the first and second pressing means is adjusted in such a way that the fluff after the second pressing means contains more moisture than the fluff after the first pressing means, and pure chemicals and soft water are added as a supplement to the soft finishing bath in such amounts that the volume of the soft finishing bath remains constant. In this case, the moisture means water and substances dissolved in water. The mode of operation according to the invention will result in a reduction of the volume of the soft finishing bath if no chemicals and soft water are added.
In another preferred embodiment of the invention, the pH of the wash liquor in the last wash zone is between 5.0 and 6.0 and the pH of the soft finishing bath is below 7.5, preferably between 6.0 and 7.5. The acidic pH in the final wash liquor surprisingly enables more water to be removed by squeezing, thereby reducing entrainment and avoiding flooding in the soft finishing bath.
Claims (4)
1. A method of manufacturing modal fibers, comprising at least the following method steps:
a. preparing alkali cellulose from a cellulose raw material,
b. the alkali cellulose is aged and the resultant is then,
c. the mixture is subjected to xanthation and acidification,
d. the mixture is dissolved and then is added with water,
e. curing, filtering, degassing,
f. the spinning bath is used for spinning the fiber,
g. stretching the mixture to obtain a stretched mixture,
h. post-treatment (including cutting, bleaching, washing, finishing, drying, opening, packaging),
i. the recovery of the chemicals is carried out by,
wherein the finishing step in the post-treatment consists of at least a final wash zone, a first extrusion device, a soft finishing bath and a second extrusion device, wherein the finishing step is operated on a separate conveyor belt in such a way that the intake of liquid into the soft finishing bath after the first extrusion device is less than the output of liquid after the second extrusion device.
2. The method of claim 1, wherein the soft finishing bath is operated without overflowing.
3. A method according to claim 1, wherein the line pressure of the first and second pressing means is adjusted in such a way that the fluff after the second pressing means contains more moisture than the fluff after the first pressing means, and pure chemicals and soft water are added as a supplement to the soft finishing bath in such amounts that the volume of the soft finishing bath is kept constant.
4. The process according to claim 1, wherein the pH of the wash liquor in the last wash zone is between 5.0 and 6.0 and the pH of the soft finishing bath is below 7.5, preferably between 6.0 and 7.5.
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