US20080048358A1 - Lyocell Method Comprising an Adjustment of the Processing Duration Based on the Degree of Polymerization - Google Patents
Lyocell Method Comprising an Adjustment of the Processing Duration Based on the Degree of Polymerization Download PDFInfo
- Publication number
- US20080048358A1 US20080048358A1 US11/569,061 US56906105A US2008048358A1 US 20080048358 A1 US20080048358 A1 US 20080048358A1 US 56906105 A US56906105 A US 56906105A US 2008048358 A1 US2008048358 A1 US 2008048358A1
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- US
- United States
- Prior art keywords
- cellulose
- degree
- solution
- polymerization
- suspension
- 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
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000012545 processing Methods 0.000 title claims abstract description 20
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 19
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- 238000004519 manufacturing process Methods 0.000 claims description 19
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- 108010059892 Cellulase Proteins 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 86
- 150000003512 tertiary amines Chemical class 0.000 abstract description 24
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- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- VTGXVUQXDHXADV-UHFFFAOYSA-N 1-methyl-1-oxidopiperidin-1-ium Chemical compound C[N+]1([O-])CCCCC1 VTGXVUQXDHXADV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- MMAXOAIHEPNELR-UHFFFAOYSA-N n,n-dimethylcyclohexanamine oxide Chemical compound C[N+](C)([O-])C1CCCCC1 MMAXOAIHEPNELR-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
- B29B7/905—Fillers or reinforcements, e.g. fibres with means for pretreatment of the charges or fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92314—Particular value claimed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92323—Location or phase of measurement
- B29C2948/92361—Extrusion unit
- B29C2948/92409—Die; Nozzle zone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92809—Particular value claimed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
Definitions
- the invention relates to a method of producing Lyocell fibres, in which a cellulose is introduced with a predetermined degree of polymerisation, and from the cellulose, with the addition of a treatment medium, a cellulose solution or initially a cellulose suspension and from this then the cellulose solution is produced, and in which the cellulose solution is extruded to form endless moulded bodies.
- the invention also relates to a device for the production of Lyocell fibres with a mixing device to which a cellulose can be fed and in which a cellulose solution, with the addition of a treatment medium, directly or with the formation of a cellulose suspension can be processed, with a spinning head, through which the cellulose solution can be extruded to form endless moulded bodies, and with a conveying device, through which the cellulose suspension and/or the cellulose solution can be conveyed from the mixing device to the spinning head.
- Lyocell technology threads, fibres, films and membranes are extruded as endless moulded bodies from the spinning mass containing cellulose, water and tertiary amine oxide. Due to its environmental compatibility, the Lyocell technology is increasingly replacing the conventional viscose methods.
- the environmental compatibility of the Lyocell method is based on the solution of the cellulose without derivatisation in an organic, aqueous solvent. From this cellulose solution endless moulded bodies are extruded, for example fibres and films.
- Lyocell was issued by the BISFA (International Bureau for the Standardisation of Man-made Fibres). In the state of the art, the Lyocell method is now well documented.
- Tertiary amine oxides are known as solvents for cellulose from U.S. Pat. No. 2,179,181 which can dissolve cellulose without derivatisation. From these solutions, the cellulose moulded bodies can be obtained by precipitation.
- NMMNO N-methylmorpholine-N-oxide
- N-methylpiperidine-N-oxide N-methylpyrolidone oxide, dimethylcyclohexylamine oxide and others can be used as the amine oxide.
- Mixing in the mixing chamber occurs between 65° C. and 85° C.
- the cellulose is mixed in a device with the aqueous solution of the tertiary amine oxide, whereby the mixing device exhibits a mixing tool and a container which rotates during mixing.
- the mixing tool is improved such that it is formed as a paddle, rail or helix and during mixing preferably prevents the formation of deposits on the inner surface of the container.
- a buffer device is described, which comprises a mixing vessel and a conveying screw as a discharging device. In this way, a continuous production of the cellulose solution is facilitated despite the cellulose being fed in batches.
- WO-A-96/33934 has been further developed by the method of WO-96/33221, in which a homogeneous cellulose suspension is produced from pulverised cellulose and an aqueous amine oxide solution in one single step.
- the pulverised cellulose is brought into contact with the liquid, aqueous tertiary amine oxide and a first mixture is formed in this way.
- the first mixture is spread in layers on a surface and transported under intensive mixing over this surface. This process can be carried out continuously.
- Other methods in which the cellulose solution is treated in the form of a thin layer are also known from EP-A-0356419, DE-A-2011493 and WO-A-94/06530.
- pulverisation of the cellulose itself is an object of patent publications.
- U.S. Pat. No. 4,416,698 mentions it as an advantage if the cellulose is milled to a particle size of less than 0.5 mm.
- prepulverised cellulose is introduced into an aqueous solution of a tertiary amine oxide to produce a first suspension. This first suspension is then milled and converted into a formable cellulose solution with the application of heat and a reduced pressure.
- filters are used in WO-A-94/28215 through which the cellulose dust is separated from the air.
- WO-A-96/38625 a system is described which can pulverise both cellulose bales as well as cellulose in leaf form.
- an ejection hopper is provided which opens into a device for prepulverising the cellulose.
- the system NMMNO/cellulose/water in the highly concentrated NMMNO region has the property of releasing metal ions from the process apparatus, such as lines, filters, and pumps, which reduces the system stability.
- WO-A-96/27035 a method for the production of cellulose moulded bodies is described in which at least some of the materials in contact with the cellulose solution contain at least 90% of an element from the group of titanium, zirconium, chrome and nickel down to a depth of at least 0.5 ⁇ m.
- the important aspect with regard to WO-A-96/27035 is that the rest of the composition of the apparatus and piping, where it comes into contact with the cellulose solution, does not contain any copper, molybdenum, tungsten or cobalt. According to WO-A-96/27035, this measure should prevent exothermic decomposition reactions.
- DE-A-44 39 149 Another way of producing the cellulose solution is followed in DE-A-44 39 149 which forms the closest state of the art.
- the cellulose is pretreated enzymatically.
- the cellulose can be disintegrated before the pretreatment under shearing in water.
- the pretreated cellulose is separated from the liquor and the separated cellulose is introduced into a melt of NMMNO and water.
- the separated liquor can practicably be fed back to the pretreatment after supplementing the water and enzyme losses.
- this type of process management has proven to be impracticable, because the cellulose solution obtained in this way is unstable.
- the object of the invention is therefore to improve the known methods and devices of the Lyocell technology such that, with the highest environmental compatibility, the method can be implemented independent of the type of cellulose used in a stable manner and with consistently constant quality.
- This object is solved for the aforementioned method in that the degree of polymerisation of the cellulose, the cellulose suspension and/or the cellulose solution is monitored and that, in dependence of the determined degree of polymerisation, the residence period of the cellulose from its introduction to its extrusion is set.
- this object is solved according to the invention by a monitoring device, through which a degree of polymerisation of the cellulose, the cellulose suspension and/or the cellulose solution can be monitored during the operation of the device, and by a control device, through which the processing duration from the introduction of the cellulose to its extrusion in the spinning head can be set in dependence of the measured degree of polymerisation.
- the solution according to the invention is simple and enables any type of cellulose to be used in the production of Lyocell fibres irrespective of its degree of polymerisation. Due to the control, according to the invention, of the processing or residence duration of the cellulose from its pulping through to its extrusion to give endless moulded bodies, a uniform quality of the Lyocell fibres is obtained irrespective of the degree of polymerisation of the processed cellulose. Since additionally, the degree of polymerisation is monitored according to the invention during the processing of the cellulose, it is no longer necessary to only process carefully selected celluloses. According to the invention, any cellulose can now be processed, because a change of the degree of polymerisation in the cellulose, the cellulose suspension and/or the cellulose solution during the processing can be acquired and the processing duration adapted accordingly.
- the method according to the invention and the device according to the invention can both be used with the Lyocell method in which the cellulose is directly pulped in an aqueous solution of a tertiary amine oxide or in a tertiary amine oxide and cellulose solution is produced from it, and also with methods in which first a cellulose suspension is produced containing essentially water and cellulose and only then is a tertiary amine oxide or an aqueous solution of it added to form a cellulose solution.
- the cellulose or the cellulose suspension is subjected to an enzymatic pretreatment.
- a liquid enzyme preparation can, for example, be added in the ratio of 200:1 referred to the cellulose content.
- a cellulase enzyme complex for example Cellupract AL70 from the company Biopract GmbH, or Cellusoft from the company Novo Nordisk, can be used.
- the duration of the enzymatic pretreatment can be set in dependence of the degree of polymerisation of the introduced cellulose.
- the degree of polymerisation can also be monitored during the enzymatic pretreatment and the duration of the enzymatic pretreatment can be shortened if the degree of polymerisation is strongly reduced.
- the enzymatic pretreatment can be carried out in a pulper.
- the known parameters (Newton's number, Reynold's number, Froude's number) in the agitating technology can first be determined. Furthermore, the concentrations, temperatures, mixing times and the mixing quality can be accurately observed and determined in order to obtain information about the decomposition behaviour during the formation of the emulsion or suspension.
- the temperature control can be carried out via temperature measurement devices, e.g. of type Pt100. The exact concentration can be set using continuous flow measurement devices for the emulsion or suspension agent. The cellulose can be accurately measured using a differential dosage weighing system and similarly continuously charged.
- the suspension criteria such as filling level, agitation duration and concentration of the emulsion/suspension particles over the container height can be determined by the insertion of a measurement sampling lance into the suspension vessel or pulper or into the agitating machine and by the sampling of suspended material. It has been found to be particularly advantageous if the form of the bottom of the suspension vessel is realised as a dished or spherical bottom.
- An impeller agitator is preferably used as the stirring element.
- propellers, inclined blade mixers, disc mixers, toothed stirrers, anchor stirrers as well as spiral stirrers or coaxial agitating machines can also be used.
- the shaft of the stirring machine which is connected to a drive motor is controlled and monitored for speed. Similarly, the monitoring of the drive power, the input energy and the torque takes place during the emulsion and suspension processes for the control of the enzymatic breakdown of the cellulose and thus for the control of the degree of polymerisation using at least one sensor.
- the degree of polymerisation of the cellulose, the cellulose suspension and/or the cellulose solution can be determined by inline sensors such as torque sensors with associated software and control with computation of the relative reduction in viscosity. These types of systems are, for example, offered by the company PORPOISE. Alternatively, the degree of polymerisation can be determined by manual sample extraction followed by analytical determination of the degree of polymerisation, which however reduces the degree of automation for the method.
- inline sensors for example strain gauges, fitted between the drive motor and agitating machine or eddy current sensors, can be used for the measurement of power and torque.
- the eddy current measurement is based on the principle that the permeability for magnetic field lines is modified by mechanical stresses.
- the magnetic field generated by a stationary sensor head penetrates the agitator drive shaft and induces electrical voltages in the secondary coils of the sensor head in relation to the mechanical stress which are proportional to the torque. The measurement takes place without contact and free of any reactive forces.
- a prerequisite for the use of this method in the suspension production system is that a free, accessible piece of the shaft is available on the drive side of the agitating machine to which the sensor can be aligned.
- the degree of polymerisation can be determined via the viscosity according to the cuoxam method.
- the measurements and the measurement signals from the inline sensors are calibrated with the analytical results, correlated and are used for the process control and are to be preferred over a manual sample extraction, because they facilitate the automation of the control of the residence duration.
- the enzymatic pretreatment is realised over a shorter time period than for a cellulose with a higher degree of polymerisation, for example of at least DP 700.
- the enzymatic pretreatment can last between 20 minutes and 80 minutes, whereby the degree of polymerisation after the termination of the enzymatic pretreatment does not drop below a DP value of 520. If the DP value falls below 520, the enzymatic pretreatment is terminated. Then follows the production of the cellulose solution through the vaporisation of water from the enzymatically broken down cellulose and the aqueous tertiary amine oxide. Also in this process step further DP breakdown can be monitored via inline sensors such as for example an inline viscosity device, e.g. from Porpoise, and can be controlled in conjunction with the enzymatic DP breakdown behaviour. In this respect the rheometer is mounted in a branch of the pipe carrying the mass.
- the cellulose solution can be transported to the spinning head by a heated pipe system. Since a reduction in the degree of polymerisation also occurs in the course of this transport, the transport speed of the cellulose solution in the pipe system can be set in relation to the degree of polymerisation of the cellulose solution, of the preceding cellulose suspension and/or the introduced cellulose which is dissolved in the cellulose solution.
- the lower the degree of polymerisation of the cellulose solution the faster the cellulose solution is transported to the spinning head according to the invention in order to prevent the extrusion of endless moulded bodies with a degree of polymerisation which is too low.
- the duration of processing the cellulose solution until its extrusion can be set in a particularly easy way in an advantageous embodiment in that the transport speed of a pump arrangement transporting the cellulose suspension and/or cellulose solution is set in relation to the degree of polymerisation.
- the processing duration of the cellulose from its introduction through to its extrusion to form endless moulded bodies is preferably set such that it is at the most 80 minutes and/or at least 20 minutes. In this time frame, a good solution of the cellulose in the tertiary amine oxide can be achieved and at the same time the degree of polymerisation cannot fall below values which lead to an impaired quality of the Lyocell fibres.
- FIG. 1 an embodiment of a device according to the invention for the production of a cellulose solution in a schematic illustration, whereby the method according to the invention can be implemented;
- FIG. 2 a schematic illustration of the steps of the method for the production of the cellulose suspension
- FIG. 3 a schematic illustration of the change of the quantity of iron ions borne out over time
- FIG. 4 a schematic illustration of the chemical oxygen demand in the press water over time
- FIG. 5 a schematic illustration of a first method for the control of the metal ion content
- FIG. 6 a schematic illustration of the power transfer of an agitating machine for a cellulose suspension over the residence time
- FIG. 7 a schematic illustration of the reduction in the degree of polymerisation over the residence time for the cellulose suspension.
- FIG. 1 shows a plant 1 for the production of endless moulded bodies 2 , for example spinning filaments, from a spinnable cellulose solution containing water, cellulose and tertiary amine oxide.
- cellulose in the form of leaves or plates 3 and/or rolls 4 is passed to a pulper 5 in batches.
- the cellulose 3 , 4 is treated with water as a treatment medium, symbolically represented by the arrow 6 , and a cellulose suspension is formed, preferably still without solvent or amine oxide.
- Enzymes or enzyme solutions can be added for the homogenisation and stabilisation of the cellulose suspension.
- the quantity of the added water 6 is determined in relation to the water content of the cellulose.
- the water content of the cellulose used is between 5 and 15 percent by mass. This variation is compensated by changing the addition of water appropriately, so that the water content of the cellulose suspension or the bath ratio of solids/liquid remains approximately constant or attains a freely selected value.
- the cellulose suspension is passed through a thick matter pump 7 via a pipe system 8 to a press device 9 , whereby the cellulose suspension of water and cellulose is preferably maintained in a temperature range from 60 to 100° C.
- the cellulose suspension produced by the pulper 5 is for example expressed by rotating rolls 10 .
- the expressed water or press water 11 is collected by a collecting device 11 ′ and passed back to the pulper 5 by a conveying means 12 , through an optional filter device 13 and through a mixing device 14 at least in part as water 6 .
- the press device 9 can also be fitted with a suction device (not shown) for drawing off excess water from the cellulose suspension.
- the drawn-off water is passed back, as the press water, at least in part to the pulper 5 .
- drawn-off water or water removed from the cellulose suspension by other means is also press water which can be recycled for the treatment or disintegration of the cellulose.
- the filter 13 can comprise one or more surface filters, deep-bed filters, membrane filters, plate filters, edge filters, separators, centrifuges, hydrocyclones, belt filters and vacuum belt filters, tube filters, filter presses, rotating filters, reversible-flow filters, multilayer filters and also flotation methods.
- the press water 11 can be osmotically treated in the filter 13 ; alternatively or additionally metal ions and particles can be filtered out of the press water 11 or metal-binding additives can be fed to the press water 11 .
- the respective proportions of the returned treatment medium 11 and of fresh treatment medium 15 , for example fresh water, fed from another fresh source are adjusted by a mixing device 14 in the water passed to the pulper 5 .
- the proportion of the treatment medium 11 which is passed or discharged out of the plant 1 through a waste water pipe 16 , is set by the mixing device 14 .
- the mixing device 14 can for example comprise a selector valve or a number of valves.
- the mixing device 14 is controlled by a control device 17 such that the proportions of the press water 11 and of the fresh water 15 in the water 6 fed to the pulper 5 can be set to variably specifiable values in response to an output signal from the control device via at least one control line 18 .
- the cellulose suspension is transported further through the pipe system 8 to a stirring and conveying means 19 in which a shear stress acting on the cellulose suspension is generated by a stirring or conveying tool 20 , such as screws, paddles or blades.
- a stirring or conveying tool 20 such as screws, paddles or blades.
- no annular layer mixers can be employed, such as originating from DRAIS Misch- und Matterssysteme and sold under the designation CoriMix®.
- the annular layer mixers are only used for moistening or impregnating dry cellulose materials which are not used in the method described here.
- a treatment medium such as tertiary amine oxide, in particular N-methylmorpholine-N-oxide, is supplied to the cellulose suspension in aqueous form with a molar ratio NMMNO/H 2 O of between 1:1 and 1:2.5 as solvent for the cellulose via a pipe 21 .
- additives such as stabilisers and enzymes, organic additives, delustering substances, alkalis, solid or liquid earthy bases, zeolites, finely pulverised metals such as zinc, silver, gold and platinum for the production of anti-microbial and/or electrically or thermally conducting fibres during and after the spinning process and/or dyes can be added to the cellulose suspension in the shear zone.
- concentration of the additives can be controlled in the range from 100 to 100,000 ppm referred to the fibre product.
- the concentration of the supplied NMMNO depends on the water content of the celluloses 3 , 4 currently in the cellulose suspension.
- the stirring and conveying means 19 acts as a mixer in that the tertiary amine oxide is mixed with the cellulose suspension and the cellulose solution is produced. Then the cellulose solution to which NMMNO has been added is transported via the pipe system 8 to a second stirring and conveying means 22 .
- the stirring and conveying means 22 can comprise a vaporisation stage. From the stirring and conveying means 22 on, the pipe system can be heated. In contrast to the unheated pipe system 8 , the heated pipe system in FIG. 1 is given the reference symbol 8 ′.
- a pipe system can be used, as described in WO 01/88232 A1, WO 01/88419 A1 and WO 03/69200 A1.
- Conveying devices 7 ′ in the form of pumps can be arranged both in the pipe system 8 as well as in the pipe system 8 ′ to transport the cellulose suspension and/or the cellulose solution.
- the metal ion content of the cellulose solution, in particular copper and iron ions, in the pipe 8 ′ and/or in at least one of the shear zones 19 , 22 , or before and/or after one of the shear zones is measured using the sensors 23 , and a signal representing the metal content or the content of individual destabilising metal ions, such as iron, chrome, copper and/or molybdenum is output to the control device 17 .
- the metal ion content can in a further embodiment be determined after a manual sample extraction using wet-chemical methods in an automatic laboratory analysis device and passed on from there to the control device 17 automatically or manually.
- the feedback to the controller for the metal ion content contains a manual process stage and cannot therefore be automated.
- the control device 17 compares the metal ion content measured by the sensors 23 with predetermined limits and outputs a signal depending on this metal ion content to the mixing device 14 . Due to the control signal to the mixing device 14 , the composition of the water 6 as treatment medium passed to the pulper 5 is set in dependence of the content of the destabilising metal ions of the cellulose solution, and the metal content or the content of individual metal ions in the cellulose solution to which tertiary amine oxide has been added is regulated under closed-loop control to a predetermined value. Since the concentration of reactions in the cellulose solution increases after the vaporisation stage, preferably a sensor is provided which monitors the metal content of the cellulose solution after the addition of all constituents and after all the vaporisation stages.
- the metal content of destabilising metal ions in the cellulose solution is too high, then the proportion of fresh water in the water 6 fed to the pulper 5 is increased.
- the metal content is then adjusted by the control device 17 such that it remains below a stability limit of 10 mg/kg.
- the metal content can also be determined before the formation of the cellulose solution, i.e. still in the cellulose suspension, whereby this measurement is more appropriate than the measurement of the metal content directly in the cellulose solution.
- sensors 23 devices for atomic absorption measurement mass spectrometers, optical detectors for the acquisition of fluorescence spectra, emission spectra or Raman scattering can be used. These types of sensor are known and are produced by various manufacturers, for example by Perkin Elmer.
- the degree of polymerisation of the cellulose suspension and/or the cellulose solution can be determined via inline sensors 23 ′, for example from the company PORPOISE, the number of which is as required, for example via a viscosity measurement.
- inline sensors 23 ′ a sample can be taken manually at the corresponding point and its degree of polymerisation be found in the normal way, for example according to the cuoxam method.
- sensors 23 ′ sensors can be used which monitor the power transferred by agitating machines, such as torque sensors, eddy current sensors or strain-gauge sensors.
- the sensors 23 ′ for the degree of polymerisation are arranged in the pulper 5 and in the pipe system 8 , 8 ′.
- the measured degree of polymerisation is passed in signal form to the control device 17 .
- the inline sensors are rheometers from the company PORPOISE.
- the control device 17 takes into account the previously determined metal content of the cellulose 3 , 4 passed to the pulper 5 .
- the analysed metal content of individual metal ions or the complete content of metal in the cellulose 3 , 4 just used can be entered into the control device 17 and/or its degree of polymerisation via an input device 24 .
- the preadjustment or present default value of the metal content is taken into account in the determination of the proportions of the press water and fresh water in the water fed to the pulper 5 . For example, with cellulose having a high metal content a higher proportion of fresh water 15 is passed to the pulper 5 at the start or certain metal-binding additives are mixed into the cellulose suspension.
- the metal content decreases, as it is acquired by the sensors 23 in the cellulose solution to which tertiary amine oxide has been added, below a certain limit which is taken as sufficient for protection against exothermic reactions, for example 10 mg/kg, then the proportion of press water in the water passed to the pulper 5 is increased. Consequently, with sufficient protection against exothermic reactions, less fresh water is consumed and less press water is discharged to the environment.
- the control device 17 also controls the residence or processing period of the cellulose 3 , 4 in the plant 1 in dependence of the degree of polymerisation as entered manually into the input device 24 or, during operation, determined by the sensors 23 ′ or by means of manually extracted samples analysed in the laboratory.
- the sensors 23 ′ and/or the laboratory analysis devices for the samples extracted manually act as monitoring devices for the degree of polymerisation.
- the processing duration of the cellulose from its introduction into the pulper 5 through to its extrusion in an extrusion head 25 is set such that close to the extrusion head 25 , shortly before the extrusion of the cellulose solution, the degree of polymerisation does not fall below 450 DP, preferably not below 550 DP.
- the control device 17 controls in particular the conveying device 7 which empties the pulper 5 .
- the pretreatment and prepulping are shortened by operating the pump 7 at an earlier time.
- the conveying capacity of the further pumps 7 ′ in the pipe systems 8 , 8 ′ is increased.
- the duration of the pretreatment in the plant 1 takes, for example with celluloses 3 , 4 having a high degree of polymerisation of at least 600 DP, about 40 minutes, and, with celluloses 3 , 4 having a relatively low degree of polymerisation of 400 DP and less, at the most 25-30 minutes.
- the now extrudable cellulose solution is passed to the extrusion head 25 , which is fitted with a large number of extrusion openings (not shown).
- the highly viscous cellulose solution is extruded through each of these extrusion openings to form an endless moulded body 2 into an air gap 26 .
- An orientation of the cellulose molecules occurs due to a drawing of the cellulose solution which is still viscous after the extrusion.
- the extruded cellulose solution is drawn off the extrusion openings by a take-off mechanism 27 with a speed which is greater than the extrusion speed.
- the endless moulded bodies 2 cross a precipitation bath 28 containing a non-solvent such as water, whereby the cellulose in the endless moulded bodies 2 is precipitated.
- the endless moulded bodies 2 are cooled by a cooling gas flow 29 .
- the cooling gas flow does not impinge on the endless moulded bodies 2 immediately after the exit of the endless moulded bodies 2 from the die, but rather at a distance from the die.
- the cooling gas flow should be turbulent and exhibit a velocity component in the extrusion direction, as described in WO 03/57951 A1 and in WO 03/57952 A1.
- the precipitation bath 28 becomes increasingly enriched with tertiary amine oxide, so that it must be continuously regenerated using a recovery device 30 .
- the liquid from the precipitation bath is fed to the recovery device 30 via a pipe 31 , which for example is connected to an overflow on the precipitation bath.
- the recovery device 30 removes the tertiary amine oxide from the liquid and returns purified water via a pipe 32 . Waste substances that cannot be recycled are ejected from the device 1 via a pipe 33 and taken for disposal.
- the amine oxide is separated from the water and passed via a pipe 34 to a further mixing device 35 , to which fresh amine oxide is fed via a pipe 36 .
- the regenerated amine oxide from the pipe 34 is mixed with the fresh amine oxide 36 and passed via the pipe 21 to the shear zone 19 .
- Metal ions can be removed from the regenerated amine oxide by an ion exchanger, for example from the company Rohm und Haas, Amberlite GT 73 or filters 37 .
- the mixing device 35 and the purification device 37 can be controlled by the control device 17 in dependence of the metal ion content as measured by the sensors 23 .
- the endless moulded bodies are treated further, for example washed, brightened, chemically treated in a device 38 to influence the cross-linking properties, and/or dried and pressed out further in a device 39 .
- the endless moulded bodies can also be processed by a cutting device, which is not shown, to form staple fibres and passed in non-woven form from the device 1 .
- All of the conveyance of the cellulose solution in the pipe system 8 ′ occurs continuously, whereby buffer containers 40 can be provided in the pipe system 8 ′ to take up variations in the conveyed amount and/or of the conveying pressure and to facilitate continuous processing without the occurrence of dead water regions.
- the pipe system 8 ′ is equipped with a heating system (not shown) to maintain the cellulose solution during conveyance at a temperature at which the viscosity is sufficiently low for economical transport without decomposition of the tertiary amine oxide.
- the temperature of the cellulose solution in the pipe section 8 ′ is between 75 and 110° C.
- the high temperature promotes the homogenisation and uniform mixing, which can be increased by static or rotating mixers.
- the residence time of the cellulose suspension or solution in the pipe system 8 , 8 ′ from the thick matter pump 7 through to the extrusion head 25 can be, depending on the degree of polymerisation of the processed cellulose and with the use of special additives for the cellulose suspension and cellulose solution, between 5 minutes and 2 hours, preferably about 30 to 60 minutes.
- the implementation of the method according to the invention is now described based on experimental examples.
- the parameters (Newton's number, Reynold's number, Froude's number) known in agitation technology were determined.
- the concentrations, temperatures, mixing times and mixing quality were exactly observed and determined in order to obtain information about the breakdown or decomposition behaviour during the formation of the emulsion or suspension.
- the exact adjustment of the concentration occurred through continuous flow measurement devices for emulsion or suspension agents, and the addition of the cellulose also occurred continuously, exactly measured via a differential dosage weighing system.
- the suspension criteria such as filling level, stirring duration and concentration of the emulsion/suspension particles over the container height were determined by inserting a measurement sampling lance and the extraction of suspended material. An impeller stirrer was used as the stirring element.
- propellers inclined blade mixers, disc mixers, toothed stirrers, anchor stirrers as well as spiral stirrers or coaxial agitating machines can also be used.
- the shaft of the stirring machine which is connected to a drive motor is controlled and monitored for speed.
- the monitoring of the drive power, the input energy and the torque occurs during the emulsion and suspension stages for the control of the enzymatic breakdown of the cellulose and thus for the control of the degree of polymerisation.
- a first series of experiments involved the cellulose pretreatment for the production of the cellulose suspension and the examination of the press water.
- the schematic illustration of the pretreatment in FIG. 2 and also the reference symbols of FIG. 1 are used.
- cellulose 3 , 4 (cf. FIG. 1 ) of type MoDo Dissolving Wood Pulp, pine sulphite wood pulp, was placed in a pulper 5 from the company Grubbens having a net filling volume of 2 m 3 with water 6 in a mixing ratio of 1:17 (solid density 5.5%).
- the cellulose exhibited a cuoxam DP of 650 and an ⁇ -cellulose content greater or smaller than 95%.
- Commercially available celluloses based on hardwood or softwood can be used. Hemicellulose contents in the cellulose in the range from 2 to 20% can also be processed in the method.
- celluloses Sappi Eucalyptus, Bacell Eucalyptus, Tembec Temfilm HW, Alicell VLV and Weyerelle ⁇ -cellulose of less than 95%.
- the fed water 6 consisted of 30 parts of fully desalinated fresh water 15 and 70 parts of press water.
- the pretreatment was interrupted in a process step B by the addition of sodium hydroxide solution (soda lye) 52 in the ratio of 1:500 referred to the cellulose content of the cellulose suspension in the pulper 5 .
- the cellulose suspension was then dehydratised to about 50% in a process step C in a vacuum belt filter acting as press means 9 followed by an expressing system from the company Pannevis, so that the expressed cellulose exhibited a dry content of about 50%. From step C, the expressed cellulose was then passed on via the pipe 8 for production of the cellulose solution containing NMMNO, water and cellulose. These steps are not shown in FIG. 2 for the sake of clarity.
- the press water was collected in the press means 9 and led away via the pipe 11 (cf. FIG. 1 ). Approximately 75% of the press water was fed back to the pulper 5 and about 25% of the press water was passed via the pipe 16 to a waste water purifier.
- the degree of polymerisation of the cellulose was always selected such that a DP (degree of polymerisation) of about 450 to about 550 was obtained in the spinning solution.
- the cellulose concentration was set to about 12% in the spinning solution.
- the press water remaining in the system 1 was again mixed in a mixing device 14 (cf. FIG. 1 ) in a process step D with the fully desalinated water, as described above.
- the press water collected during the expressing stage was analysed for copper and iron ion content and additionally the chemical oxygen demand was determined.
- the percentage proportion of the iron extracted from the system 1 may be between 22% and 35% referred to the quantity of iron introduced by the cellulose.
- FIG. 3 gives a schematic temporal trace of the iron ion extraction.
- the chemical oxygen demand was determined in the press water according to DIN 38409 and approximates with increasing duration of the press water feedback to a constant value.
- the cellulose solution obtained through press water feedback is stable and exhibits an onset temperature of at least 160° C.
- the onset temperature shown in Table 1 according to the method with press water return according to the invention is also above the onset temperature as it is obtained by the method of WO 95/08010, and in practice is about 150° C.
- the press water feedback is suitable for industrial use.
- the iron and copper content as well as the metal ion content of the cellulose overall varied noticeably with the various types of cellulose, as can be seen from Table 2.
- the metal content of the various types of cellulose was determined by incineration in the platinum crucible according to DIN EN ISO 11885 (E22) and with flame AAS.
- FIG. 5 the reference symbols of FIGS. 1 and 2 are used for elements with similar or the same function.
- the iron ion and copper ion content was measured as representative values for the metal ion content by the sensors 23 , 23 ′ (cf. FIG. 1 ).
- the iron concentration was maintained as closely as possible below 10 mg/kg absolutely dry and the copper concentration just below 0.5 mg/kg absolutely dry.
- the setting of the metal ion content according to the invention can also be achieved via the tertiary amine oxide recovered from the spinning bath 28 .
- the degree of purification on the metal ion filter 37 and/or the proportion of the tertiary amine oxide 36 freshly added to the regenerated tertiary amine oxide 34 can be set in dependence of the metal ion content as measured by the sensors 23 and 23 ′, as well as in dependence of the metal ion content previously found in the cellulose 3 , 4 .
- the control functions similarly as with the press water feedback.
- recovered water from the spinning bath 28 can be returned instead of or together with the press water to the pulper 5 .
- the metal ion filter 37 as it is used in the recovery of the tertiary amine oxide from the spinning bath 28 , can of course also be used for the purification of the returned press water.
- the reduction in the degree of polymerisation can be prevented in a simple manner if the duration of the enzymatic treatment is set such that for example a degree of polymerisation of at least 590 DP to 600 DP is present at the end of the enzymatic treatment. Furthermore, the transport of the cellulose suspension and/or the cellulose solution can be speeded up such that a degree of polymerisation of at least 550 DP is obtained before the extrusion of the cellulose solution.
- the starting cellulose was selected with a DP of 780 and the enzyme concentration was increased by the factor 0.5. Furthermore, the power consumption of the agitating machine was also recorded during the activation step and scaled to the container volume and the solids concentration. Table 4 shows the figures measured when carrying out the experiment.
- FIG. 6 illustrates the trace of the power in kilowatts per kilogram of cellulose applied by the agitating machine over the treatment period of the cellulose suspension in the agitating machine
- FIG. 7 shows the change of the degree of polymerisation in the agitating machine.
- the degree of polymerisation reduces with increasing treatment time for the cellulose suspension.
- the reduction in the degree of polymerisation can be seen from the clearly reduced power applied by the agitating machine. With a reduced degree of polymerisation the power applied in the agitating machine also reduces.
- the power of the agitating machine can be used as a representative quantity for the degree of polymerisation in the control of the degree of polymerisation.
- the same method for monitoring the degree of polymerisation is also possible with the following agitating machines. If, for example, the power of the agitating machine falls under a certain predetermined value, e.g. a limit determined by experiments, this is a sign that the degree of polymerisation is falling or has fallen below a figure specified for this processing stage. As a consequence, the remaining residence time of the cellulose suspension and/or the cellulose solution in the process step is shortened.
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DE102004024030.2 | 2004-05-13 | ||
DE200410024030 DE102004024030A1 (de) | 2004-05-13 | 2004-05-13 | Lyocell-Verfahren mit polymerisationsgradabhängiger Einstellung der Verarbeitungsdauer |
PCT/EP2005/002088 WO2005113868A1 (fr) | 2004-05-13 | 2005-02-28 | Procede lyocell comprenant un reglage de temps de traitement sur la base du degre de polymerisation |
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US11/569,061 Abandoned US20080048358A1 (en) | 2004-05-13 | 2005-02-28 | Lyocell Method Comprising an Adjustment of the Processing Duration Based on the Degree of Polymerization |
US12/776,737 Active US8317503B2 (en) | 2004-05-13 | 2010-05-10 | Device for producing Lyocell fibers |
US13/659,649 Active US8580167B2 (en) | 2004-05-13 | 2012-10-24 | Lyocell method comprising an adjustment of the processing duration based on the degree of polymerization |
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US13/659,649 Active US8580167B2 (en) | 2004-05-13 | 2012-10-24 | Lyocell method comprising an adjustment of the processing duration based on the degree of polymerization |
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EP (1) | EP1747307B1 (fr) |
KR (1) | KR100798213B1 (fr) |
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AT (1) | ATE401436T1 (fr) |
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Cited By (6)
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US20050220916A1 (en) * | 2002-01-08 | 2005-10-06 | Stefan Zikeli | Spinning device and method having turbulent cooling by blowing |
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AT505492B1 (de) * | 2007-07-11 | 2014-06-15 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von cellulosischen formkörpern unter verwendung von bambuspapierzellstoff und formkörper aus diesem verfahren |
CN103510180A (zh) * | 2013-09-17 | 2014-01-15 | 上海婉静纺织科技有限公司 | Lyocell竹纤维及其制备方法 |
CN105037753B (zh) | 2015-06-01 | 2017-12-05 | 中国纺织科学研究院 | 一种纤维素溶液的制备工艺及其设备 |
EP3536850A1 (fr) * | 2018-03-06 | 2019-09-11 | Lenzing Aktiengesellschaft | Pulpe et articles en lyocell avec un taux en cellulose réduit |
EP3741887A1 (fr) * | 2019-05-21 | 2020-11-25 | Aurotec GmbH | Procédé et dispositif de régénération d'un solvant de la cellulose provenant d'un procédé de filature |
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Also Published As
Publication number | Publication date |
---|---|
TW200604397A (en) | 2006-02-01 |
CN100547129C (zh) | 2009-10-07 |
KR20070012851A (ko) | 2007-01-29 |
DE102004024030A1 (de) | 2005-12-08 |
TWI297742B (en) | 2008-06-11 |
US8317503B2 (en) | 2012-11-27 |
US20100219547A1 (en) | 2010-09-02 |
KR100798213B1 (ko) | 2008-01-24 |
EP1747307B1 (fr) | 2008-07-16 |
EP1747307A1 (fr) | 2007-01-31 |
DE502005004737D1 (de) | 2008-08-28 |
US8580167B2 (en) | 2013-11-12 |
US20130049244A1 (en) | 2013-02-28 |
CN1981075A (zh) | 2007-06-13 |
WO2005113868A1 (fr) | 2005-12-01 |
ATE401436T1 (de) | 2008-08-15 |
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