Process for producing a pulp

Abstract

The invention relates to a process for producing a dissolving pulp from a cellulosic starting material using the kraft process, comprising the step of cooking the starting material with a cooking liquor. The process according to the invention characterized in that the starting material is exposed to a steam treatment prior to cooking and that the pulp obtained by cooking is subjected to cold caustic extraction (CCE) in the course of further processing.

Claims

1. A process for producing a lyocell fiber from a dissolving pulp, comprising the step of cooking a cellulosic starting material with a cooking liquor in a kraft process to obtain the dissolving pulp, wherein the cellulosic starting material is exposed to a steam treatment prior to cooking, wherein the steam treatment consists of applying a temperature of 120 C. or more and a P-factor of 50 or less, wherein the dissolving pulp obtained by cooking is subjected to cold caustic extraction (CCE) in the course of further processing whereby a CCE treated dissolving pulp is formed, and wherein the lyocell fiber having a content H of hemicellulose of more than 3.5% by weight and less than 5% by weight is produced from the CCE treated dissolving pulp.

2. The process according to claim 1, further comprising treating the dissolving pulp obtained by cooking to adjust the degree of polymerization (DP).

3. The process according to claim 1, wherein, for the steam treatment, the cellulosic starting material is treated with medium-pressure steam at a temperature of from 150 to 180 C.

4. The process according to claim 1, wherein the cellulosic starting material is subjected to an impregnation prior to cooking.

5. The process according to claim 1, wherein the cooking, the steam treatment and optionally an impregnation of the cellulosic starting material are carried out in the same cooker.

6. The process according to claim 1, wherein the cooking is carried out in a form of continuous batch cooking (CBC).

7. The process according to claim 1, wherein at least a portion of a press liquor formed in the cold caustic extraction is purified using a membrane separation process.

8. The process according to claim 7, wherein the membrane separation process is nanofiltration.

9. The process according to claim 7, wherein the membrane separation process is an ultrafiltration.

10. The process according to claim 1, wherein at least one of a portion of a press liquor formed in the cold caustic extraction and a portion of a retentate of a membrane separation process performed on the press liquor is supplied to the cooking liquor of a linked cooking process carried out for the production of paper pulp.

11. The process according to claim 1, further comprising bleaching the pulp obtained by cooking.

12. The process according to claim 1, wherein the cooking step of the pulp is carried out in two stages, and wherein, in a first stage, a delignification using a first cooking liquor to a kappa number of from 35 to 70 in case of softwoods as the cellulosic starting material and to a kappa number of from 30 to 60 in case of hardwoods as the cellulosic starting material is carried out and, in a second stage, the cooking is continued to the desired degree of purity of the pulp, using a second cooking liquor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Below, the present invention is explained in further detail based on the figures and examples.

(2) FIG. 1 shows a diagram of the basic concept of the process according to the invention and its applicabilities.

(3) FIG. 2 shows a plot of intrinsic viscosity versus kappa number of single and two-stage CBC cookings of whitewood.

(4) In FIG. 3, temperature and hydroxide ion profiles of single and two-stage softwood-CBC cookings are illustrated.

(5) FIG. 4 shows a plot of total yield versus kappa number of single and two-stage Eucalyptus globulus CBC cookings with and without accumulation of hemicellulose.

(6) FIG. 5 shows a plot of intrinsic viscosity number versus kappa number of single and two-stage Eucalyptus globulus CBC cookings with and without accumulation of hemicellulose.

(7) FIG. 6 shows the molar mass distribution of Eucalyptus globulus kraft pulps.

(8) FIG. 7 shows the comparison of the molar mass distribution of a CBC* pulp with that of a VISCBC pulp.

(9) FIG. 8 shows the strengths of standard Viscose fibres produced from various pulps in the conditioned state.

(10) FIG. 9 illustrates the influence of the ozone amount used and the radiation dose on the DP-degradation of CBC and LH sulfite pulps which have been pretreated differently.

(11) FIG. 10 shows the molar mass distribution of a CBC pulp which has been degraded to an intrinsic viscosity number of 440 ml/g by means of EBeam and ozone.

(12) FIG. 11 shows the molar mass distribution of a xylan isolated in mineral acid from a CCE filtrate by reverse precipitation.

(13) FIG. 12 shows the molar mass distribution of the xylans isolated from pulps and fibres produced therefrom by means of DMSO (graphical evaluation of the GPC analysis).

(14) FIG. 13 contrasts the intensity of the preferred steam treatment (CBC*) according to the invention with a prehydrolysis process (VISCBC). The P-factor of the steam treatment preferred according to the invention is below 50; the P-factor of the VISCBC prehydrolysis amounts to 700.

DETAILED DESCRIPTION OF THE INVENTION

(15) In FIG. 1, the basic concept of the process according to the invention and the various applicabilities thereof are illustrated schematically.

(16) Variant A shows the production of a paper pulp having a high strength potential: for this purpose, a two-stage kraft process (as a batch process or, e.g., as a CBC process) is combined with a TCF or ECF bleaching sequence. The two-stage operation permits optimum adjustment of the cooking conditions to the respective requirements.

(17) Variant B shows the concept of the production of a high-yield paper pulp (a pulp with an increased hemicellulose content): For this purpose, the process proceeds basically identically to variant A. In this case, however, the cooking liquor for the second stage of cooking is enriched with high-molecular hemicellulose from a liquor rich in hemicellulose. Said liquor rich in hemicellulose may result in particular from a CCE process which is carried out in a process C for the production of a high-yield Lyocell pulp, which process is linked to process B. The liquor rich in hemicellulose may be, for example, (a) the CCE filtrate or (b) the retentate of a nanofiltered CCE filtrate.

(18) The variant C already mentioned in FIG. 1 results in a high-yield Lyocell pulp for the production of Lyocell fibres having the highest possible textile-mechanical strength properties: The basic scheme proceeds according to variant A. However, the cooked pulp is treated either directly after washing and sorting or after each bleaching or depolymerization step (DEPOLY), respectively, preferably after an O-stage, in a CCE refining stage.

(19) In combination with a paper pulp production occurring parallel thereto, see scheme B, CCE filtrate may be used for the fortification of white liquor, preferably in the second cooking stage.

(20) If the paper pulp production is absent or too low, the liquor can be recycled via nanofiltration after purification. The permeate (b) is returned to the CCE stage, hemicelluloses can be obtained from the retentate (c).

(21) Variant D in FIG. 1 shows a preferred embodiment of the process according to the invention for the production of high-yield dissolving pulps, those are in particular

(22) (a) viscose pulp for fibres having high textile-mechanical properties,

(23) (b) all other dissolving pulps which are derivatized into cellulose ester or ether.

(24) The basic scheme proceeds according to variant C. In order to improve the pulp reactivity, the wood is subjected to a steam activation treatment (DA stage) in which the composite structure of the wood is loosened a lot with the aim of selectively separating the low-molecular hemicelluloses in the subsequent alkaline cooking.

EXAMPLES

Example 1

Two-stage CBC Cooking of Whitewood

(25) Whitewood is cooked to pulp with kappa numbers of between 16 and 42 in a test cooker of 10.8 l according to the CBC process (continuous batch cooking). The single-stage reference cooking has the following conditions: Impregnation: [OH]=0.37 mol/l, [HS]=0.22 mol/l; mean temperature 120 C., 30 min (filling direction from below to above) Heating: Displacement of the impregnating liquor by a preset cooking liquor (direction of displacement from above to below). After 28 minutes, the target temperature of 160 C. is reached. Cooking stage: Cooking liquor is pumped through the cooker from above to below at a flow rate of twice the cooker volume per hour: 160 C., [OH]=0.62 mol/l, [HS]=0.30 mol/l, H-factors: 800-1600.

(26) Impregnation and heating of the two-stage CBC cooking according to the invention were carried out along the lines of the single-stage variant. Cooking stage 1: 160 C., [OH]=0.48 mol/l, [HS]=0.48 mol/l, H-factor=750=constant Cooking stage 2: 160 C., [OH]=0.62 mol/l, [HS]=0.32 mol/l, the H-factor was varied from 100 to 600.

(27) Two variants of the two-stage CBC cooking were carried out, the difference between them was merely the concentration of dissolved substances: a) DS80 g/l (standard) b) DS40 g/l (low solid-CBC)

(28) The test results are summarized in FIG. 2 on the basis of a selectivity plot (intrinsic viscosity number versus kappa number). The results show that the already high selectivity of the single-stage CBC cooking can be improved further by the two two-stage variants.

(29) In FIG. 3, temperature and hydroxide ion profiles of the above-described single and two-stage softwood-CBC cookings are illustrated.

(30) As shown in FIG. 3, a two-stage operationin case of identical degrees of delignificationdoes not result in a prolongation of the cooking time. The hydroxide ion concentration in the cooker outlet shows a rapid increase in the course of the second cooking stage and reaches the target concentration already after half of the cooking time that has been chosen.

Example 2

Two-stage CBC Cooking of Eucalyptus globulus

(31) Eucalyptus globulus is processed into pulp with kappa numbers of between 13 and 28 in a test cooker of 10.81 according to the CBC process (continuous batch cooking).

(32) The single-stage reference cooking (one-stage) has the following conditions: Impregnation: [OH]=0.38 mol/l, [HS]=0.25 mol/l; mean temperature 120 C., 30 min (filling direction from below to above) Heating: Displacement of the impregnating liquor by a preset cooking liquor (direction of displacement from above to below). After 30 minutes, the target temperature of 155 C. is reached. Cooking stage: Cooking liquor is pumped through the cooker from above to below at a flow rate of twice the cooker volume per hour: 155 C., [OH]=0.65 mol/l, [HS]=0.34 mol/l, H-factors: 200-500.

(33) Impregnation and heating of the two-stage CBC cooking (two-stage) were carried out along the lines of the single-stage variant. Cooking stage 1: 155 C., [OH]=0.46 mol/l, [HS]=0.37 mol/l, H-factor=180=constant Cooking stage 2: 155 C., [OH]=0.62 mol/l, [HS]=0.37 mol/l, the H-factor was varied from 100 to 400.

(34) In a second variant, the cooking liquor of the second stage was produced with the hemi-rich filtrate of a CCE treatment.

(35) Thereby, the conditions in cooking stage 2 were adjusted as follows: 155 C., [OH]=0.37 mol/l, [HS]=0.16 mol/l, beta-cellulose concentration (from CCE filtrate)=10 g/l, H-factor=150-400.

(36) As is evident from FIG. 4, the yield could be considerably improved in the entire kappa number range for both the simple two-stage variant (two-stage) and the two-stage variant reinforced with hemicellulose (hemi-add) in comparison to the single-stage mode of operation.

(37) The advantage of the two-stage process control also reveals itself in the digestion selectivity, which is illustrated in FIG. 5 as the plot of intrinsic viscosity number versus kappa number.

(38) What is remarkable is that the cooking selectivity, i.e., the intrinsic viscosity at a particular kappa number, is very high after all CBC cookings in comparison to Eucalyptus globulus cookings produced in a conventional manner.

Example 3

Production of High-yield Dissolving Pulps for Further Processing into Viscose and Lyocell Fibres

(39) Prior to the beginning of CBC cooking, the wood was exposed to steam activation (DA) by bringing the content of the cooker to a temperature of approx. 165 C. with the aid of medium-pressure steam. CBC cooking was carried out in a single stage.

(40) For better identification, the combination of the processes DA+CBC is subsequently indicated by CBC*. After O-delignification, CBC* pulp was subjected to a cold caustic extraction with the aim of removing the hemicelluloses soluble in alkali. DP-adjustment was effected by ozone treatment (Z) within the scope of final bleaching. The subsequent P-bleaching served for the stabilization of the cellulose and for the adjustment of the desired final degree of whiteness. As a reference pulp, a prehydrolysis kraft pulp was produced by means of VISCBC technology (modified visbatch process, see Wizani, W, et al. CBCContinuous batch cooking. The revolution in kraft cooking in Pulping process and product quality conference, 2000, Boston, Mass., USA).

(41) The following table 1 shows the most important characteristics of unbleached pulps.

(42) TABLE-US-00001 TABLE 1 Characterization of unbleached E. globulus pulps: CBC* pulp (paper pulp) and VISCBC cooking process, as a reference for a conventional dissolving pulp. CBC* VISCBC Parameters Wood #134 #141/142 P-Factor 0 490 Yield, sorted % 100.0 52.9 37.2 Cellulose yield % wood 46.1 41.0 34.9 Kappa number 13.1 6.0 Intrinsic viscosity ml/g 1281 963 Whiteness % ISO 37.7 42.8 R18-20 C. % pulp 92.6 96.9 R18-50 C. % pulp 84.4 96.2 Xylan % pulp 16.0 18.4 3.1 % wood 16.0 9.7 1.1

(43) Thereby, the P-factor expresses the intensity of prehydrolysis. The calculation is based on the same concept as with the H-factor, with a different activation energy (123 kJ/mol) being used.

(44) The yield (cellulose content) of the CBC* pulp was higher by 15.7 percentage points (6.1 percentage points) in comparison to the VISCBC reference pulp (see Table 1).

(45) Subsequently, the bleaching of the CBC* and VISCBC pulps was finished with the aid of an OZP-TCF sequence. In order to reduce the low-molecular hemicelluloses, the CBC* pulps were subjected to a cold caustic extraction after O-delignification (CCE stage).

(46) The CCE treatment was carried out at two different NaOH concentration levels, 50 g/l and 100 g/l. A white liquor having a sulfidity of 26% served as an alkali source. All other conditions such as temperature (30 C.), residence time (30 min) and stock density (10%) were kept constant in both experiments.

(47) Final bleaching was performed in all pulps with the aid of a Z-P-sequence, wherein the object of ozone bleaching consisted primarily in adjusting the DP to the level for regenerated pulps (DP of 950-1200, corresponding to an intrinsic viscosity number GVZ of 420-500 ml/g). The most essential process and pulp data (within the scope of pulp bleaching) are listed in the following Table 2.

(48) TABLE-US-00002 TABLE 2 Characterization of bleached high-yield E. globulus-CBC*-CCE dissolving pulps and, as a reference, a bleached VISCBC dissolving pulp. CBC* reference CBC*-CCE50 CBC*-CCE100 VISCB reference Parameters Units O Z P O CCE Z P O CCE Z P O Z P Conditions Temperature C. 110 50 80 110 30 50 70 110 30 50 70 110 50 80 Residence time min 60 240 60 30 120 60 30 120 60 300 Stock density % 12 10 10 12 10 10 10 12 10 10 10 12 10 10 NaOH charge kg/t 25 12 25 6 25 6 25 9.3 NaOH concentration g/1 50 100 O2 partial pressure bar 10 10 10 10 Ozone charge kg/t 11.87 6.8 3.5 2.8 Peroxide charge kg/t 10 5 5 6 Pulp parameters Total yield %/wood 51.7 50.83 50.3 51.7 47.1 46.9 46.6 51.7 45.2 45.1 44.9 36.6 36.4 36.2 Kappa number 7.7 1.2 0.5 7.7 4.5 0.5 0.3 7.7 2.9 0.4 0.3 1.8 0.4 0.2 Whiteness % ISO 66.4 84 89.0 66.4 90.2 92.5 66.4 91.4 93.6 70.2 88.2 92.4 Intrinsic viscosity ml/g 893 498 470 893 984 490 475 893 1026 490 465 650 490 455 R18-20 % 93.1 96.1 96.4 98.7 97.8 97.0 Xylan % 17.3 9.6 9.3 4.7 4.2 2.9

(49) From Table 2 it becomes clear that the CCE treated CBC* pulps exhibit an R18 level which lies in the range of high-grade finished prehydrolysis kraft pulps (VISCBC reference). In contrast, the yield of bleached CBC*-CCE materials is by 8.7-10.4 percentage points higher than that of the reference pulp.

(50) The advantage in yield can largely be traced back to the higher cellulose content. The higher xylan content (alkali resistant) of CBC*-CCE pulps also contributes to the higher yield, with said proportion decreasing with an increasing NaOH concentration in the CCE stage.

(51) A simple balance shows that the CCE treatment removes non-cellulosic polysaccharides very selectively, whereas an intensive prehydrolysis also causes a massive breakdown of cellulose.

(52) An important criterion for the assessment of dissolving pulps, especially with regard to their properties of further processing, is the molar mass distribution.

(53) The molar mass distribution of Eucalyptus globulus kraft pulps is illustrated in FIG. 6.

(54) The upper part of FIG. 6 shows unbleached CBC pulps which were produced according to a two-stage CBC cooking process. The Willis CBC two-stage and CBC hemi-add thereby refer to pulps produced according to Example 2 with and without accumulation of hemicellulose. The graph -xylan refers to xylan isolated from the CCE stage in an isolated manner.

(55) The lower part of FIG. 6 illustrates the following pulps: (a) CBC*: unbleached CBC pulp after steam activation (b) CBC*depoly: CBC* after TCF bleaching (c) CBC*-CCE: CBC* after CCE treatment at a NaOH concentration of 100 g/l (d) (c) TCF bleached.

(56) The molar mass distribution was determined via GPC in a LiCl/DMAc and MALLS detection [Schelosky, N., T. Rder, and T. Baldinger, Molecular mass distribution of cellulose products by size exclusion chromatography in DMAC/LiCl. Das Papier, 1999. 53(12): p. 728-738].

(57) The lower part of FIG. 6 clearly shows that the CCE treatment removes the low-molecular carbohydrate fraction very effectively and selectively.

(58) A comparison with the molar mass distribution of conventional, high-grade finished dissolving pulps, which were produced according to a prehydrolysis kraft process (VISCBC), shows (see FIG. 7) that the CCE treatment with the higher NaOH concentration level enables a narrower distribution (lower polydispersity) than in case of the reference pulps. In FIG. 7, a VISCBC pulp is compared to a CBC* CCE100 Depoly pulp as a CBC* pulp which has undergone a CCE process with 100 g/l of NaOH and has been subjected to a depolymerization treatment (TCF bleaching).

(59) Further Processing into Regenerated Fibres

(60) 1. Viscose Fibres:

(61) An important criterion for the further processing of dissolving pulps is the achievable viscose quality which has been evaluated on the basis of the filter value according to Treiber [Sixta, H., et al., Evaluation of new organosols dissolving pulps. Part I: Preparation, analytical characterization and viscose processability. Cellulose, 2004. 11(1): p. 73-83.], the average particle content and the particle distribution in an order of magnitude of 3-150 m (determination with the aid of a PAMAS measuring instrument [Sixta et al., Cellulose, 2004. 11(1): p. 73-83]).

(62) The following Table 3 shows that the steam activation treatment prior to CBC cooking constitutes the critical step for improving the resulting viscose quality. The subsequent CCE treatment leads to a further improvement of the viscose quality, whereby, as expected, the effect increases with a rising NaOH concentration.

(63) TABLE-US-00003 TABLE 3 Viscose quality, measured on the basis of the filter value and the average particle volume of reference and test pulps Particle volume Pulps # Filter value ppm VISCBC reference 73/05 364 28 CBC reference 14/05 34 156 CBC* 74/05 180 58 CBC*-CCE50 75/05 223 34 CBC*-CCE100 15/05, 7/06 306 28

(64) Table 3 shows that the quality of the viscose produced from the CBC*-CCE100 pulp is almost equivalent to that of the one produced from the VISCBC reference pulp. The viscoses were filtered and spun on a laboratory spinning machine with 20 hole ( 50 m) at a total of 4 different stretch ratios.

(65) The strengths of the produced standard Viscose fibres in the conditioned state are summarized in FIG. 8. Therein, fibres from a) CBC paper pulp b) CBC*-CCE pulp and a c) VISCBC reference pulp are contrasted with each other.

(66) The results prove that the CBC*-CCE pulp is as good as the reference dissolving pulp (VISCBC), as far as a further processing into Viscose fibres is concerned. The slightly smaller fibre elongations can be traced back to a less complete filtration which is noticeable from a slightly increased amount of small particles in an order of magnitude of between 5 and 10 m.

(67) In the following table, the chemico-physical properties of the pulps used and of the Viscose fibres produced therefrom (according to a standard spinning process) are contrasted with each other:

(68) TABLE-US-00004 TABLE 4 Chemico-physical properties of the pulps and of the Viscose fibres produced therefrom (standard quality). Pulps produced according to the invention Reference Parameters Pulp 1 Pulp 2 Solucell Type Units CBC*-CCE100 CBC*-CCE100 PHK Pulp Bl 269 Bl276 FEZ 1167 Wood species E. globulus E. globulus E. urograndis Whiteness % ISO 93.0 92.6 89.6 Viscosity ml/g 441 411 421 R18 % 98.1 98.4 97 R10 % 96.5 96.8 93.35 Xylan % 6.4 4.3 2.9 Mannan % 0.4 0.5 0.0 ZS Viscose fibre Xylan % 3.8 2.8 0.7 Mannan % 0.3 0.2 0.0 Hemicellulose total % 4.1 3.0 0.7 Titre dtex 1.3 1.3 1.3 Tenacity (cond) at 50% stretching cN/tex 23.8 24.3 23.9 at 60% stretching cN/tex 25.0 25.6 25.2 at 70% stretching cN/tex 25.8 25.7 25.7 at 80% stretching cN/tex 25.1 25.1 24.5 Elongation at 50% stretching % 18.7 19.8 20.5 at 60% stretching % 16.8 18.2 19.4 at 70% stretching % 15.3 16.1 17.4 at 80% stretching % 13.8 14.5 15.4 Yield of mercerization % 94.8 96.7 n.d.

(69) The pulp Solucel is a VISCBC pulp.

(70) According to the invention, the content of hemicellulose is understood to be the sum of non-glucose-containing sugar ingredients (calculated as anhydro sugar) following a total hydrolysis (two-stage hydrolysis with sulfuric acid) of the pulp or the fibre, respectively. The measurement is performed via anion-exchange chromatography combined with a pulsed amperometry as a detection method. The measurement methodology is described in U. Mais, H. Sixta, ACS Symposium Series 2004, 864, 94, as well as in H. Sixta et. al. Proceedings of the 11th ISWPC 2001, vol. 3, pp. 655-658.

(71) Method of Determining the Yield of Mercerization:

(72) De-Finishing:

(73) The fibres are extracted with 96% EtOH on a Soxhlet extractor for 3 h and dried under vacuum at 50 C. over night.

(74) Yield of Mercerization:

(75) 2.00 g of de-finished fibres (initial weight M.sub.1) is vigorously stirred (pestled) at 20 C. with a glass rod with 50 mL NaOH, having a concentration of 250 g/L, in a beaker for 3 minutes. Subsequently, the fibre slurry is sucked off via a G3 fit and washed neutrally with VE water. After the fibre has been dried, the fibre is weighed again (output weight M.sub.2). The yield of mercerization is the quotient from M.sub.2/M.sub.1 (%).

(76) Lyocell Fibres:

(77) It is known that depolymerized kraft paper pulp is suitable for the production of high-quality Lyocell fibres [WO 99/47733]. An (optionally two-stage) kraft cooking with steam preactivation creates the basis for the production of Lyocell fibres with considerably better textile-mechanical properties. The results of spinnings in a Davenport laboratory spinning plant prove that a cold caustic extraction of kraft paper pulps raises the textile-mechanical properties to the level of Lyocell fibres made of the highest-quality dissolving pulps (VISCBC) (Table 5).

(78) TABLE-US-00005 TABLE 5 Strength properties of Lyocell fibres produced from CBC paper and dissolving pulps with the aid of a Davenport laboratory spinning plant Conditioned fibre data, 1.3 dtex Strength Pulps # cN/tex Elongation % VISCBC reference L66 40.7 12.7 CBC reference L32 30.0 10.1 CBC*-CCE50 L53_54 36.0 12.5 CBC*-CCE100 L22 41.0 10.4

(79) The following table compiles the result of further experiments for the production of Lyocell fibres made of different pulps:

(80) TABLE-US-00006 TABLE 6 Chemico-physical properties of the pulps and of the Lyocell fibres produced therefrom Pulps produced according to the invention Reference Parameters Pulp 1 Pulp 2 High Hemi Solucell Type Units CBC*-CCE100 CBC*-CCE100 Kraft PHK Pulp Bl 269 BL294 ZF1761 FEZ147/99 Wood species E. globulus Beech Southern Pine E. urograndis Whiteness % ISO 93.0 92.7 88.8 90.2 Viscosity ml/g 441 350 451 415 R18 % 98.1 97.3 86.9 96.9 R10 % 96.5 95.1 82.9 Xylan % 6.4 4.7 8.5 3.3 Mannan % 0.4 0.2 5.6 0.0 Hemicellulose total 6.8 4.9 14.1 3.3 Lyocell fibre Laboratory Pilot plant Pilot Laboratory Xylan % n.d. 4.1 7.8 3.1 Mannan % n.d. 0.2 5.3 0.0 Hemicellulose total 4.3 13.1 2.9 Fibre properties Titre dtex 1.3 1.3 1.3 1.3 Tenacity (cond) cN/tex 41.0 39.7 31.7 42.7 Elongation % 10.4 11.8 11.7 12.7 Yield of mercerization % n.d. 95.2 86.7 96.4

(81) The pulp High Hemi is a pulp corresponding to the teaching of WO 99/47733. The pulp Solucell is a VISCBC pulp.

(82) It is evident from the table that the Lyocell fibres spun from pulps produced according to the invention (CBC*-CCE100) exhibit excellent properties with regard to the fibre strength and the yield of mercerization comparable to those of Lyocell fibres made of a high-quality VISCBC pulp, despite a cheap production of the pulp and a higher hemicellulose content.

(83) The Lyocell fibres according to the invention clearly exceed the properties of fibres produced from a pulp corresponding to the teaching of WO 99/47733.

Example 4

Controlled DP-adjustment of High-yield Dissolving Pulps

(84) In laboratory tests, the behaviour of ozone bleaching and electron irradiation (Beam) with regard to the DP-degradation of OP-(CCE)-A and OP-(CCE)-D, respectively, prebleached CBC, CBC*-CCE50 and CBC*-CCE100 pulps was compared to each other. By way of comparison, a softwood sulfite pulp (LH sulfite) was also exposed to electron irradiation.

(85) Ozone bleaching was thereby carried out by mixing in a high-shear mixer under fluidizing conditions, in each case with a stock density of 10% and a pH of 2.0.

(86) The EBeam treatment was performed at an accelerating voltage of 10 MeV in a Rhodotron Accelerator by Messrs. IBA SA, Louvain-La-Neuve, after the pulp sheets had been dried.

(87) All pulps were subjected to peroxide bleaching after the Z or EBeam treatment, respectively (70 C., 10 kg NaOH/t, 7 kg H2O2/t, 120 min, 10% stock density, 0.5 kg Mg II ions/t).

(88) The results in FIG. 9 show that the extent of the chain cleavages (KSP, calculated according to formula 10.sup.4/P.sub.j-10.sup.4/P.sub.0 (PDPv calculated from SCAN GVZ values; .sub.j . . . after degradation, .sub.0 . . . prior to degradation)) depends very strongly on the concentration of hemicelluloses (and also lignin, not illustrated) in the pulp as a function of the ozone amount used. The higher the hemicellulose content, the higher the ozone charge for achieving a particular KSP.

(89) The CBC-CCE100 pulp low in hemicellulose requires only about 3 kg O.sub.3/t for a KSP of 5.6 (GVZ degradation from 750 ml/g to 420 ml/g), whereas a CBC pulp with a xylan content four times as high (see Table 2) requires more than 12 kg O.sub.3/t for the same degrading effect.

(90) The electron irradiation is different, however: The dose required for a particular DP-degradation is largely independent of the type and the composition of the pulp.

(91) Table 7 confirms the stabilizing effect of an alkaline peroxide treatment following the degradation processes on the basis of the copper number and carboxyl group contents. After both degradation processes, the P-stage brings about an additional KSP of approx. 0.6-1.2, depending on the respective conditions.

(92) TABLE-US-00007 TABLE 7 Copper number and carboxyl group content of CBC*- CCE100 pulps following a Z, EBeam or subsequent alkaline peroxide bleaching, respectively OP-CCE100-A-Z-P Z P Copper no. % 0.85 0.72 COOH mmol/kg 34 37 OP-CCE100-D-Ebeam-P Ebeam P Copper no. % 0.79 0.65 COOH mmol/kg 33 40

(93) The advantage of the electron irradiation manifests itself in the clearly narrower DP distribution of the finished pulps. FIG. 10 shows that the CBC paper pulp depolymerized by means of EBeam exhibits a considerably narrower distribution than a CBC pulp broken down with ozone. With a degradation to a GVZ of 440 ml/g, the polydispersity index (PDI) amounted to 4.3 in case of the Z-treated pulp and amounted only to 3.5 in case of the EBeam-treated pulp. In each case, the analysis was performed on the finished pulp after a final P-stage.

Example 5

Production of High-yield Paper Pulp

(94) The use of a cooking liquor rich in hemicellulose in the second cooking stage causes primarily an increase in the pulp yield. As is explained in Example 2, the average yield increase (at a hemi-concentration of approx. 10 g/l in the cooking liquor) is approx. 2 percentage points in comparison to the single-stage variant across a wide kappa number range (see FIG. 4).

(95) The reprecipitation of xylan on the pulp surface is clearly identifiable as an increase in the low-molecular fraction in the molar mass distribution, see upper part of FIG. 6, and influences both the surface properties and the mechanical strengths. The high uronic acid content (GlcA) of the xylans (Xyl), GlcA:Xyl ratio approx. 0.05:1, causes an increase in the hydrophilicity of the pulp surface.

Example 6

Production of Xylan Products

(96) 1. Isolation of Xylan from the CCE Filtrate

(97) With the aid of a pilot nanofiltration plant (NF) equipped with a polyethersulfone membrane, Nadir N30 F, cut-off 300, a CCE filtrate was prefiltered using a cartridge filter (Profile Star AB1A4007J) in order to filter out remaining fibres and undissolved particles.

(98) The NF plant was operated at a temperature of 40 C., a pressure of 25 bar and a specific flow rate of 5 l/m.sup.2.Math.h. The beta-cellulose (xylan) concentration in the feed amounted to approx. 15 g/l, the NaOH concentration was 90 g/l. The ratio of flow and hence also the liquor loads in the permeate to the retentate were 0.82:0.18.

(99) Due to the low cut-off of the membrane, the total amount of beta cellulose in the retentate was at a concentration of about 85 g/l. The retentate was diluted with water at a ratio of 1:1.5 and again was supplied to the NF.

(100) The NF conditions of the second stage were comparable to those of the first stage, with the exception that the amount of permeate dropped to about 70% of the feed amount. In the retentate of the second NF stage, the beta cellulose was now present at a concentration of about 115 g/l and at a NaOH concentration of about 32 g/l (hemi liquor).

(101) Said substrate served for the isolation of the beta-cellulose (xylan) by reverse precipitation with mineral acid. For this purpose, approximately 0.1 parts of a sulfuric acid diluted 1:3 with water were mixed with 1 part of hemi liquor, whereby a pH of between 4 and 5 appeared in the end.

(102) After about 6-8 h, an off-white precipitate with a consistency of approx. 10-15% by weight forms. Said precipitate was then centrifuged, washed and dried. A xylan content of 74% by weight was detected in this solid substance. Based on the total carbohydrate content, the xylan content amounted to 97.5%. The molar mass distribution of said xylan powder as determined by GPC shows a weight-average molecular mass of 24.4 kg/mol and a number-average molecular mass of 10.6 kg/mol (see FIG. 11).

(103) 2. Further Processing of the Xylan Powder into Xylo-Oligosaccharides (XOS)

(104) XOS was produced from the xylan in two ways, (A) hydrothermolytically, (B) enzymatically:

(105) (A) Hydrothermolytic XOS Production:

(106) 318 g of dry xylan was diluted in 9.08 L water (xylan concentration 35 g/L) and was treated in an 11 L-pressure reactor at 120 C. for 5 h under continuous circulation. The circulation flow rate was 75 L/h. Upon completion of the reaction, the pH value of the hydrolysate was 3.13.

(107) Subsequently, the solution was neutralized with 0.3 N NaOH to pH 6.5-7.0. The water-soluble products were spun down at 4000 U/min for 60 min. The isolated amount of XOS was 189.7 g of a freeze-dried powder, corresponding to a yield of 59.6%, based on the xylan used. The XOS mixture produced hydrothermolytically exhibits a relatively uniform composition across the examined DP-range (see bottom part of Table 8).

(108) (B) Enzymatic Hydrolysis:

(109) XOS.sub.2-10

(110) 90 g of wet xylan (equal to 40 g of dry xylan) was suspended in 900 mL water (44.4 g/L) and 50 mg Pentopan Mono BG (1.25 mg/g xylan) was added. The mixture was stirred in a fermenter at 50 C. for 2 h. Thereupon, the enzyme was inactivated by 10 minutes of heating to 99 C. The remaining insoluble portions were spun down, the aqueous solution was freeze-dried. The yield of XOS, based on the xylan used, amounted to 75%.

(111) XOS.sub.2

(112) The reaction was carried out in a 7 L-fermenter with a filling of 6 L, the xylan concentration amounted to 20 g/L (120 g xylan). The production was likewise effected with the enzyme Pentopan Mono BG, but with an increased concentration of 1 g/L (50 mg/g xylan). Fermentation was carried out at 40 C. for 96 h. Reprocessing occurred as described above. The yield of XOS amounted to 78%, based on the amount of xylan used (93.66 g XOS). The product consists primarily of xylobiose (Table 8).

(113) TABLE-US-00008 TABLE 8 Relative mass fractions of individual neutral XOS Hydro- Enzymatically Product thermally XOS.sub.2-10 XOS.sub.2 distribution % by weight X1 11.2 0.1 4.7 X2 9.7 13.0 83.1 X3 10.6 21.0 12.2 X4 12.2 16.0 X5 12.5 11.0 X6 12.0 7.9 X7 12.6 7.2 X8 10.3 7.2 X9 9.0 6.9 X10 9.7 XOS 100.0 100.1 100.0

Example 7

Molar Mass Distribution (MMV) of Hemicelluloses (Xylans), Isolated from Pulps and Fibres Produced According to the Invention

(114) The use of the new generation of dissolving pulps of category CBC*-CCE for the production of high-strength Lyocell textile fibres can be demonstrated clearly based on the molar mass distribution (MMV) of the hemicelluloses isolated from the fibres (in case of softwoods those are almost exclusively xylans) in combination with the high strengths and the high yield of mercerization.

(115) The hemicelluloses are extracted from the substrates (pulp or fibres, respectively) with the aid of DMSO according to the method of D. Evtuguin et. al. (Carboh. Res. 338 (2003) 597) and are purified. Beforehand, the fibres are also de-finished with EtOH (25 g Soxhlet with 1 L EtOH, 6 h). The isolated xylan (45 mg) is suspended in DMAc (1 mL) and dissolved in a molecularly disperse manner by adding LiCl (8 mg) at room temperature. The molar mass distribution is determined via GPC under the following conditions: solvent: LiCl/DMAc; temperature: room temperature; separating column: Mixed A from Polymer Labs; detection: MALLS (Wyatt)/RI; refractive index increment: 0.136 mL/g.

(116) The results of the MMV determination of the hemicelluloses isolated from pulps and Lyocell fibres produced therefrom are summarized in Table 9 and FIG. 12.

(117) TABLE-US-00009 TABLE 9 MMV of xylans isolated from pulps and Lyocell fibres produced therefrom by means of DMSO: numerical evaluation of weight and number average Pulp produced Conventional according to pulp Parameters the invention Solucell Type Units CBC*-CCE100 PHK Pulp BL294 ZFAT1772 Wood species Beech E. urograndis Xylan % 4.7 2.8 DMSO xylan extract Mw (GPC: LiCl/DMac) g/MoL 44,750 7,900 Mn (GPC: LiCl/DMAc) g/MoL 9,800 5,100 PDI (Mw/Mn) 4.6 1.5 Lyocell fibre Pilot plant Production Xylan % 4.1 2.9 DMSO xylan extract Mw (GPC: LiCl/DMac) g/MoL 24,700 7,200 Mn (GPC: LiCl/DMAc) g/MoL 7,850 4,500 PDI (Mw/Mn) 3.1 1.6

(118) The pulp Solucell-1772 is a VISCBC pulp.

(119) The results of GPC measurements of the xylans isolated from pulp and fibres permit the following conclusions: The profile of the xylan-MMV in the pulp is reflecteddespite a degradationin the fibre. Xylans from CBC*-CCE pulps are substantially higher-molecular and more polydisperse than those made of conventional prehydrolysis kraft pulps (PHK). Xylans from Lyocell fibres produced by using a CBC*-CCE pulp exhibit a weight average (Mw) of 20 kDa. In contrast, xylans from Lyocell fibres which originate from PHK pulps (or also sulfite pulps) which are commercial today exhibit a weight average (Mw) of 10 kDa.