• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a phase-stable suspension of cellulose-lI in water with high water retention capacity, which has a cellulose concentration between 0.1 and 5.0 wt .-%, a process for their preparation and their use.
    公开号:AT515174A1
    申请号:T796/2013
    申请日:2013-10-15
    公开日:2015-06-15
    发明作者:
    申请人:Chemiefaser Lenzing Ag；
    IPC主号:
    专利说明:

    Cellulosesueoenalon. Process for their preparation and use
    The present invention relates to a novel cellulosic suspension with cellulose I (structure, an economical process for its preparation and the use of this cellulose suspension, inter alia for the production of cellulose particles, such suspensions are often referred to as "gel" and in the present invention both terms are understood to mean the same become.
    State of the art
    It has long been known that fibers and other shaped articles can be obtained from a solution of cellulose in an aqueous, organic solvent by the so-called Lyocell method. A solvent of NMMO (N-methyl-morpholine-N-oxide) is in particular used as the solvent. used for more than twenty years on a commercial scale. Spinning pulps containing about 13% by weight of cellulose are usually used in the corresponding production plants. A preferred cellulosic raw material is pulp, but also other cellulosic raw materials such as e.g. Cotton linters can be used depending on the circumstances. All cellulosic raw materials of natural origin have a known cellulose I structure. This differs clearly from the cellulosic Il structure, which the Lyocell-treated human body finally obtained, by means of well-known X-ray diffraction methods.
    In WO2013 / 006876A1 various patents and publications are first mentioned which describe the preparation of suspensions of nanofibrillar cellulose or fibrous cellulosic pulps of cellulose. All of these products have a cellulose I structure because they were prepared without intermediate dissolution from natural cellulosic raw materials.
    Furthermore, the patent application W02013 / 006876A1 describes the preparation of a cellulosic gel with cellulose II structure from 2% Lyocell dope. For the preparation of cellulose gel from 2% Lyocell-Splnnmasse can be precipitated in a stirred reactor in water according to the prior art in a first step, the spinning mass. According to WO2013 / 006876A1, instead, the spinning mass is cooled freely below its solidification temperature and the solidified cellulose solution is comminuted to a granulate. The cellulose granules thus produced are washed NMMO-free and then comminuted with a consistency of 2% cellulose inVE water by means of wet grinding in a colloid mill. This results in a microsuspension having a stable, gel-like character. The properties of the cellulose gel are described by the water retention capacity (WRV) and particle size by laser diffraction.
    In W02013 / 006876A1, it is argued by way of example that it is not possible to produce an equivalent cellulosic suspension of the same type with the same method also from granules or fibers which were produced from a 13% instead of the 2% spinning composition according to the invention. For comparison, Table 1 shows the WRR results from W02013 / 006876A1. When using W02013 / 006876A1 processes according to the invention a 13% instead of the 2% weight of the invention according to the invention, a cellulosic suspension with a WRV of only 250% is obtained. This is in the same range as that of suspensions made by comminuting Lyocell ribbon fibers (WRV = 270%) or Saiccor pulp (WRV * 180%). In contrast, suspensions according to WO2013 / 006876A1 of 2% dope are stable without phase separation and have a WRV in the range of 800%.
    As another feature, W02013 / 006876A1 depicts the relationship between the WRV and viscosity as a function of the cellulose concentration of microsuspensions containing between 1 and 3% by weight of cellulose (see Table 4 of WO2013 / 006876A1). These values show
    Lenzing AG, PLOSSO that in the cellulose gels according to the invention of WO2013 / 006876A1, the WRV increases with increasing cellulose concentration, but also the viscosity increases so much that gels with higher cellulose concentration are practically no longer processable due to their high viscosity.
    A major disadvantage of gel preparation from 2% lyocell spinning mass is the high expense of NMMO recovery. Compared with an I3% dope, the NMMO recovery costs are more than β times higher due to the lower cellulose / NMMO ratio at 2% dope of about 1: 6. This applies to both the variable and fixed operating costs (energy costs, etc.) and the investment costs or depreciation.
    Another disadvantage is that in the existing lyocell production plants, only dope with about 13 wt .-% cellulose are produced. This means that an own production plant would have to be built for the production of 2% spinning material.
    Patent application WO02009 / 036480 A1 describes the preparation of essentially spherical cellulose II powder by grinding of lyocell-precipitated, NMMO-washed and dried cellulose granules. The resulting cellulose II powder consists of average particle sizes of 1-400 .mu.m.
    In practice, the production of cellulose particles according to WO02009 / 036480 A1 is carried out as follows: A lyocell dope is coagulated with water in a granulator to form an irregular granulate having a particle size of 0.5-1.5 mm. This granules are washed with water, NMMO-free and dried. The dry granules are ground in a first coarse grinding with impact mills or long-nip mills to particle sizes with an average diameter of 50-200 .mu.m. In a second fine grinding with jet mills, average particle sizes of at least 5 μm are then produced. This fine grinding is very time-consuming, which means that the capacities are very low and therefore very cost-intensive.
    US Pat. No. 5,014,450 describes the preparation of crosslinked cellulose II particles.
    WO 2004/043329 A2 describes the preparation and use of cellulose microbeads with a diameter of about 15 μm.
    The preparation is carried out by precipitation of the cellulose from a mixture of viscose and sodium polyacrylate, followed by acid hydrolysis.
    US Pat. No. 5,024,831 also describes spherical cellulose particles having an average diameter of 3 to 50 pm and refers to various Japanese patents for their production. The particles described therein partly consist of cellulose derivatives and cellulose II due to the precipitation from the viscose process.
    The last three publications always describe processes in which the end product, in addition to cellulose, contains other substances which are undesirable in many applications.
    task
    The object of this prior art was to provide a cellulosic suspension that is more economical to prepare and process than cellulosic suspensions of the prior art. Another object was to provide a suitable process for preparing such a suspension as well as novel uses for it, in particular those processes and uses in which there are no undesirable accompanying substances besides the cellulose.
    Description of the invention / Description
    The solution to the above-described problem is a phase-stable suspension of underivatized cellulose II in high water
    Water retention capacity (WRV), which has a cellulose concentration between 0.1 and 4.0% by weight and the viscosity (in [Pa * s] at a shear rate 50 s'1) and the water retention capacity (in%) depending on the cellulose concentration x (in wt .-%, based on the total amount of the suspension) have the following relationship: (viscosity at 50 8-1 / WRV) * 10000 < 0,4038'x2'8132
    The context describable in this manner in the suspension according to the invention is unique, especially for underivatized cellulose. Those known in the art, e.g. According to WO2013 / 006676A1, from spun masses containing 2% by weight of cellulose-II, suspensions are always well above the range bounded by this formula (see Figure 2).
    The property range according to the invention is further limited by the relationship: (viscosity at 50 s'1 / WRV) * 10000 > 0.0201 • χ2 · 3 '
    In general, the lower the cellulose concentration of the spinning mass from which they are made, the closer suspensions are to the upper limit of the range.
    A cellulose concentration in the suspension is preferably between 0.5 and 5.0% by weight, more preferably between 1.0 and 4.0% by weight.
    The suspension according to the invention differs markedly in the profile of properties, for example, from the cellulose II suspensions prepared in WO2013 / 006876A1, which are produced from 2% spinning mass, in particular by a significantly higher water retention capacity (WRV) and a lower viscosity level. This combination of properties that could be achieved for the first time in the cellulosic suspension of the present invention significantly increases both the performance of the suspension preparation and its processability. While in the prior art cellulosic suspensions the WRV increases with increasing cellulose level in the suspension, it can be used in the present invention Suspensions typically even decrease with increasing ceiluiosis content (see Figure 1).
    According to the invention, suspensions are preferred in which the viscosity (in [Pa * s] at a shear rate 50 s * 1) and the water retention capacity (in%) depend on the cellulose concentration x (in% by weight, based on the total amount of the suspension) Context: (viscosity at 50 s'1 / WRV) * 10000 < 0.3057 * χ2 · δβββ i
    Also preferred are those cellulose II suspensions having the abovementioned properties whose WRV is between 500 and 5000%, more preferably between 1000 and 4000.
    The present invention also provides a process for the preparation of a phase-stable suspension of cellulose. I in water with high water retention capacity, characterized by the following process steps: a. Preparation of a dope containing 10 to 15% by weight of cellulose according to the lyocell method, b. Precipitation of the cellulose to obtain a NMMO and cellulose-containing material, c. Washing the material until it is substantially NMMO-free, d. Enzymatic treatment of the NMMO-free washed wet material, e. Comminution in a comminution unit to obtain a coarse cellulose suspension, f. Microsizing in a high pressure homogenizer to a stable microsuspension.
    This method not only produces the above-described novel and advantageous Cellulose II suspensions, but is also much more economical than, for example, the method described in the prior art in WO2013 / 006876A1. At a cellulose concentration of less than 10% by weight of cellulose in the dope, NMMO recovery is not economical and the investment cost is too high and at a cellulose concentration of more than 15% by weight, the dope is not easily processable.
    That in step b. The material obtained may basically have different shapes. For example, these may be granules, fibers, fleece-like, fibrous or even sponge-like structures. The least expensive is the expense when - for example with an underwater granulator or a granulator - a coarse Granulathergestetlt is.
    It is preferred in step d. the enzyme used is an endoglucanase or a mixture of endo and exoglucanases. The enzyme concentration in step d. should preferably be 0.1 to 10.0 wt .-%.
    The comminution in step e. is preferably carried out in a comminution unit, such as another granulator, a colloid mill or a refiner,
    In the precipitation of lyocell spun masses with cellulose concentrations according to the invention in water or water / NMMO mixtures, the shaped bodies formed have a more or less compact outer skin structure, depending on the precipitation conditions used. These are cellulose II structures with different ratios of crystalline and amorphous regions. With the wet grinding described in WO2013 / 006876A1, for example with a Kollold mill, it was not possible to produce microsuspensions from such material obtained by precipitation of 10-15% by weight cellulose solution.
    According to the invention, a high-pressure homogenizer is used in the last comminution step. Characteristic of this type of equipment is that comminution does not occur by shear, impact or rotor-stator principles, but by spontaneous release of the high pressure grinding fluid and the cavitations and turbulences involved. The process according to the invention works particularly effectively when in step f, the pressure in the high-pressure homogenizer is between 100 and 2000 bar. To further enhance the high pressure homogenizer's effect, it should be operated in the form of a loop reactor. Particular preference is given in step f. the suspension between 1 and 10 times, preferably 1 to 4 times, passed through the high pressure homogenizer. The suspension warms up strongly. In order to avoid damage to the suspension, it may therefore be appropriate to provide a cooling possibility in the suspension circuit, for example by installing a heat exchanger.
    Commercially, the process according to the invention is of particular interest if the production of the suspension can be carried out with a dope which is suitable also for staple fiber production. Therefore, it is advantageous if in step a. of the process according to the invention, the cellulose concentration in the dope is 12 to 14% by weight.
    The present invention likewise relates to the use of the above-described suspension according to the invention for the preparation of substantially spherical cellulose particles having a cellulose II structure, a spherical shape and an average diameter x $ o of 1 to 4 pm, the formation of the cellulose particles being carried out by spray drying according to the invention.
    The use of the cellulosic suspension known from WO 2013006876 A1 (from 2% spinning mass) or other comparable cellulosic suspensions is also fundamentally possible in this case, but in most cases it is probably eliminated due to its less economical production.
    The substrate to be dried, i. the cellulosic suspension according to the invention is atomized via a nozzle into fine droplets. The droplets are discharged with the stream of hot air into a separation cyclone, thereby evaporating water. Various parameters such as the cellulose concentration, the size of the spray nozzle or the difference between supply and exhaust air temperatures can influence the particle structure. The resulting cellulose particles have an approximately spherical shape and a
    Lenzing AG, PL0550 average diameter of < 1 - 5 mm on. The approximate spherical form is expressed primarily by the axial ratio (l: d) between 1 and 2.5. The surface of the particles is irregular and clearly visible in the microscope are corners and edges; however, the particles do not show fibrous fibrils or fibrils in the microscope. So by no means is it bullets with a smooth surface.
    Principle and $ chema of spray drying are shown in Fig. 3. That is; A: Delivery of the cellulosic suspension. B: Supply of the spray air («compressed air)
    Tg: temperature measurement for the supply air TA; Temperature measurement for exhaust air1: Intake for supply air2: Electric heater3: Spray nozzle4: Spray cylinder5: Exhaust air 6: Separation cyclone 7: Exhaust air output filter 8: Collecting vessel for the dried particles
    In the following the invention will be described by way of examples. However, the invention is expressly not limited to these examples, but includes all other embodiments based on the same inventive concept.
    Examples
    Measurement of water retention capacity (WRV):
    To determine the WRV, a defined amount of suspension is introduced into special centrifuge tubes (with drainage for the water). Thereafter, centrifuging is carried out at 3000 rpm for 15 minutes and the wet cellulose is weighed immediately. The moist cellulose is dried for 4 hours at 105 ° C and then determines the dry weight. The WRR is calculated according to the following formula: WRV [%] " {mf-mt) / mn00 (nrif®mass wet, mt = dry moraine)
    Measurement of the viscosity:
    The viscosities were determined by means of a Malvern Kinexus rheometer using a Konova plate measuring system (CP4 / 40S0687 SS) at a shear rate of 50 s'1.
    BfiiSpieU ,:
    A 13% lyocell dope is coagulated with an underwater granulator in 50% NMMO as precipitation bath medium to a spherical granule, the granules separated from the precipitation vessel, washed with deionized (NM) water NMMO-free and centrifuged off the remaining wash water. The wet granules are treated at a liquor ratio of 1:15 with 1% enzyme (Endoglucanase Novozym 476) for 90 min at 60eC with gentle stirring. The enzyme is then separated, washed out and centrifuged. By briefly heating to 90 ° C, the enzyme remaining is deactivated. This granulate is then pre-ground at a stock density of 2% cellulose in deionized water with an IKAMK2000 / 10 colloid mill for 15 minutes and further formed into a microemulsion via a high pressure homogenizer GEA Niro Soavi NS 1001L-2K at 1000 bar and 4 passes. The resulting material has a WRV of 1661% and is stable for more than 2 weeks without phase separation. ß9i $ .Plel &
    A 13% lyocell dope is coagulated into irregular granules with a granulator in water as precipitating bath medium, separated from the precipitating vessel, washed with deionised water, NMMO-free, and centrifuged off from the remaining washings. The moist granules are treated at a liquor ratio of 1:15 with 1% enzyme (Endoglucanase Novozym 476) for 90 min at 60eC with gentle stirring. The enzyme is then separated, washed out and centrifuged off. By briefly heating to 90 ° C the remaining enzyme is deactivated in the wet granules. This granulate is then pre-ground at a consistency of 2% by weight of cellulose in deionized water with a colloid mill for 15 minutes and further through a high pressure homogenizer at 1000 bar and 5 passes to a microemulsion shaped. The material obtained has a WRV of 1524% and is stable for more than 2 weeks without phase separation.
    Example 3:
    A 13% lyocell dope is coagulated into irregular granules with a granulator in water as the precipitation medium, separated from the precipitation vessel, washed with deionized water, NMMO-free, and spun off from the residual wash water. The suspension of wet granules is diluted to 1.2, 3 and 4% by weight, respectively, of cellulose with deionized water. 1% enzyme (Novozym 476), based on dry cellulose, and treated in a colloid mill at 50 ° C for 90 minutes. By briefly heating to 90 ° C, the remaining enzyme is deactivated. Subsequently, the pre-ground granules are processed in a high pressure homogenizer at 1000 bar and 4 passes to a microemulsion. The resulting suspensions are stable for more than 2 weeks without phase separation. WRV and viscosity are shown in Table 1.
    Table 1: _____________
    Table 2:
    s Comparing the WRV and viscosity of the cellulosic suspensions of Example 3 with the results of WO2013 / 006876A1 (Table 4 herein, dope with 2 wt% cellulose), it can be seen that the property profiles of the samples of Example 3 differ significantly from W02013 / 006876A1 (Table 2). In Fig. 1 daso different behavior is also shown graphically.
    Fig. 2 shows the position of the suspensions according to the invention from Example 3- (solid line) compared to the boundary lines of the invention range (dotted lines, to the respective equation) and also the position of a prior art suspension, the 6 WO2013 / Q08876A1 (dashed Line).
    In the following examples, cellulose microsuspensions of different cellulose contents were dried under different conditions in a laboratory spray dryer (Büchi Mini Spray Dryer B-290). The determination of the particle size distribution of the samples obtained therefrom was carried out by means of laser diffraction in ethanol (measuring instrument from Helos).
    Example 4:
    A cellulose microsuspension according to the invention prepared according to Example 2 with 2% by weight of cellulose content was dried at 180 ° C. supply air and 62 ° C. exhaust air temperature. The nozzle greetings was 1.5 mm. The particle size analysis gave the following values: xi0 = 1.09 pm, x5o = 3.13 pm, X0O = 7.8 pm. Flg. 4 shows the particle size distribution. ßeispieLfc
    A cellulose microsuspension according to the invention prepared according to Example 2 with 0.25% by weight cellulose content was dried at 220 ° C. supply air and 124 ° C. exhaust air temperature. The nozzle size was 1.5 mm. The particle size analysis gave the following values: xio = 0.59 pm, Χδο = 2.1 pm, θθο = 11.93 pm. Fig. 5 shows the particle size distribution, Fig. 6 SEM microscope images of the particles produced. The particles have a substantially spherical but non-spherical shape with an irregular surface. The microfoto clearly shows corners and edges.
    Example· :
    A cellulose microsuspension according to the invention prepared according to Example 2 with 0.5 wt .-% cellulose content was dried at 180 ° C Zuluft- and 83eC exhaust air temperature. The nozzle size was 1.4 mm. The particle size analysis gave the following values: xios1.07 pm, X5q = 2.22 pm, X0 0 "4.91 pm. Fig. 7 shows the particle size distribution.
    BeispjftLS;
    A cellulose microsuspension according to the invention prepared according to Example 2 with 4 wt .-% cellulose content and 0.04% Sokolan PA30CL as emulsifier was dried at 180 ° C supply air and 72 ° C exhaust air temperature. The nozzle greetings was 1.4 mm. The particle size analysis gave the following values: Xio »0.76 pm, xso-2.02 pm, xeoa4.64pm. Fig. 8 shows the particle size distribution. Fig. 9, the pictorial representation in the SEM.
    权利要求:
    Claims (11)
    [1]
    1. Phase-stable suspension of cellulose-II in water with high water retention capacity, characterized in that it has a cellulose concentration between 0.1 and 5.0% by weight and its viscosity (in [Pa * s] at a shear rate 50 s'1) and their water retention capacity (in%) as a function of the cellulose concentration x (in% by weight, based on the total amount of the suspension) has the following relationship: (viscosity at 50 s'1 / WRV) * 10000 < 0,4038V'8132
    [2]
    Suspension according to claim 1, wherein the property range of the suspension is further limited by the relationship: (viscosity at 50 s'1 / WRV) * 10000 > 0.0201 V366
    [3]
    A suspension according to claim 1, wherein the viscosity and the water retention capacity depending on the cellulose concentration x preferably have the following relationship: (viscosity at 50 s'1 / WRV) * 10000 < 0.3057 * x25698
    [4]
    4. Suspension according to claim 1, wherein the WRV is between 500 and 5000%, preferably between 1000 and 4000.
    [5]
    5. A process for the preparation of a phase-stable suspension of cellulose-II in water with high water retention capacity, characterized by the following process steps: a. Preparation of a dope containing 10 to 15% by weight of cellulose according to the lyocell method, b. Precipitation of the cellulose to obtain a NMMO and cellulose-containing material, c. Washing the material until it is substantially NMMO-free, d. Enzymatic treatment of the NMMO-free washed wet material, e. Comminution in a comminution unit to obtain a coarse cellulose suspension, f. Microsizing in a high pressure homogenizer to a stable microsuspension.
    [6]
    6. The method according to claim 5, wherein in step d. the enzyme used is an endoglucanase or a mixture of endo- and exoglucanases.
    [7]
    7. The method according to claim 5, wherein the enzyme concentration in step d. 0.1 to 10.0% by weight, based on the amount of cellulose.
    [8]
    8. The method according to claim 5, wherein in step f. the pressure in the high pressure homogenizer is between 100 and 2000 bar.
    [9]
    9. The method according to claim 5, wherein in step f. the suspension is passed through the high pressure homogenizer between 1 and 10 times, preferably between 1 and 4 times.
    [10]
    10. The method according to claim 5, wherein in step a. the cellulose concentration is 12 to 14% by weight.
    [11]
    11. Use of the suspension according to claim 1 for the preparation of cellulose particles with cellulose II structure, a spherical shape and an average diameter xso of 1 to 4 pm by spray drying.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA796/2013A|AT515174B1|2013-10-15|2013-10-15|Cellulose suspension, process for its preparation and use|ATA796/2013A| AT515174B1|2013-10-15|2013-10-15|Cellulose suspension, process for its preparation and use|
    EP14835469.9A| EP3058023B1|2013-10-15|2014-11-14|Cellulose suspension, method for the production and use thereof|
    CN201480056115.0A| CN105814119B|2013-10-15|2014-11-14|Cellulosic suspension and its preparation method and application|
    US15/027,937| US9822188B2|2013-10-15|2014-11-14|Cellulose suspension, method for the production and use thereof|
    KR1020167012513A| KR102342799B1|2013-10-15|2014-11-14|Cellulose suspension, method for production and use thereof|
    JP2016521749A| JP6453868B2|2013-10-15|2014-11-14|Cellulose suspension, process for its preparation and use|
    PCT/AT2014/000203| WO2015054712A2|2013-10-15|2014-11-14|Cellulose suspension, method for the production and use thereof|
    US15/688,178| US10513564B2|2013-10-15|2017-08-28|Cellulose suspension, method for the production and use thereof|
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