| (19) |
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|
(11) |
EP 1 552 052 B1 |
| (12) |
EUROPEAN PATENT SPECIFICATION |
| (45) |
Mention of the grant of the patent: |
|
03.10.2007 Bulletin 2007/40 |
| (22) |
Date of filing: 21.08.2003 |
|
| (51) |
International Patent Classification (IPC):
|
| (86) |
International application number: |
|
PCT/SE2003/001296 |
| (87) |
International publication number: |
|
WO 2004/022842 (18.03.2004 Gazette 2004/12) |
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| (54) |
A METHOD OF PRODUCING MECHANICAL PULP AND THE MECHANICAL PULP THUS PRODUCED
VERFAHREN ZUR HERSTELLUNG VON HOLZSTOFF UND DER SO HERGESTELLTE HOLZSTOFF
PROCEDE DE PRODUCTION DE PATE MECANIQUE ET PATE MECANIQUE AINSI PRODUITE
|
| (84) |
Designated Contracting States: |
|
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
Designated Extension States: |
|
LT LV |
| (30) |
Priority: |
06.09.2002 SE 0202629
|
| (43) |
Date of publication of application: |
|
13.07.2005 Bulletin 2005/28 |
| (73) |
Proprietor: Stora Enso Aktiebolag |
|
791 80 Falun (SE) |
|
| (72) |
Inventors: |
|
- PENG, Frank
S-663 41 HAMMARÖ (SE)
- FERRITSIUS, Rita
S-791 33 FALUN (SE)
- ÄNGSAS, Ulf
S-791 74 FALUN (SE)
|
| (74) |
Representative: Johansson, Lars-Erik et al |
|
Hynell Patenttjänst AB
Patron Carls väg 2 683 40 Hagfors / Uddeholm 683 40 Hagfors / Uddeholm (SE) |
| (56) |
References cited: :
EP-A1- 0 430 915 WO-A1-92/20855 US-A- 4 891 096
|
WO-A1-89/02951 WO-A1-98/06892
|
|
| |
|
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- ZHUNG ZHONG LEE ET AL.: 'Pectic substances contribute to fiber-fiber bonding' TAPPI
vol. 65, no. 2, February 1982, pages 61 - 63, XP002974395
|
|
| |
|
| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
|
TECHNICAL FIELD
[0001] The present invention relates to a method of mechanical pulping based on cellulose
fiber material after pretreatment of the fiber material with pectinase prior to mechanical
defibration. The invention is also related to the mechanical pulp thus produced.
PRIOR ART
[0002] In mechanical pulping wood fibers are separated by mechanical defibration, typically
in a refiner or a grinder, with or without pretreatment. When pretreatment is applied,
the process can be either TMP, where thermal softening is applied; or CTMP, where
for instance sulfite is used for the sulfonation of lignin; or APMP, where alkaline
peroxide is applied resulting in a combined effect of chemical softening due to alkali
and bleaching or brightening due to peroxide. In almost all the mechanical pulping
processes, thermal treatment is employed prior to refining to soften the wood material
thus leading to reduced energy consumption as well as improved pulp strength. While
alkaline treatment is an effective treatment for reducing energy consumption, it also
induces darkening reactions that result in poorer optical properties that are essential
for paper products based on mechanical pulps. Besides, the use of alkali results in
extensive dissolution of wood material, which results in yield loss and necessitates
effluent treatment.
[0003] In addition to conventional processes, there have been efforts to apply biotechnology
to mechanical pulping. In
WO 97/40194, a mechanical pulping process using various fungi or enzymes is described. The proposed
treatment includes compression of wood chips followed by impregnation with a biological
agent prior to refiner treatment. Although a great number of fungi and enzymes are
referred to in the patent application, the biological agents used in the given examples
are limited either to fungus with ligninase activity, or to enzymes based on xylanase
activity aiming for the hemicellulose, and lipase activity specific for the wood resin.
The examples show that the enzymatic treatment can reduce the refiner energy by 4
to 10%, in addition to the energy reduction of about 4% due to the compression treatment
as compared to the reference. At the same time the strength properties of the pulp
are improved when compared at the same pulp freeness.
[0004] Another biological pulping process involving pretreatment of wood chips is based
on lignin oxidizing fungi treatment (
US 5,055,159). The refining energy consumption can be reduced by about 30% at the same freeness.
The treatment however requires long incubation time and the pulp produced has a dark
color.
[0005] Different to the above-mentioned applications, pectinase has been specifically used
in post-treatment of mechanical pulps. In
US 5,487,812 pectinase is used for alkaline bleached mechanical wood pulp. The purpose of such
treatment is however to remove pectin remaining after the pulping process in order
to reduce the source of so-called "anionic trash" which is harmful in paper machine
operation.
[0006] EP-A-0 430 915 relates to enzymes for decomposition of hemicellulose and/or cellulose, in order
to achieve a reduction in energy consumption in the production of mechanical pulp.
The example given shows the efficiency of hemicellulase in reduction of refining energy
in the treatment of a coarsely separated pulp. However, no results are shown for the
suggested use of pectinase.
[0007] WO-A-89/02951 teaches how to treat wood pieces having a length in the fibre direction of at least
100 mm, in order to achieve a better pulp strength due to fibre separation. From the
document, the skilled person can learn that compression of at least 5 MPa has such
an effect, but that the method is difficult to employ generally on chips that are
of considerably smaller size and that moreover are more or less randomly oriented
at compression.
SUMMARY OF THE INVENTION
[0008] The present invention aims at providing a method of mechanical pulping requiring
significantly reduced refining energy consumption to reach a certain pulp freeness,
or pulp strength, as compared to prior art. The invention also aims at improved optical
properties in the pulp, such as an improved brightness.
[0009] This is accomplished by the method according to the invention, as defined in the
claims.
[0010] According to the invention, the method comprises pretreatment of the comminuted cellulose
fiber material with pectinase, alone or in combination with a chelating agent, for
instance DTPA and/or sulfite, followed by mechanical defibration and refining to produce
a mechanical pulp.
[0011] Pectin is a group of amorphous polysaccharide substances in wood. Although the amount
of pectin in softwood and hardwood is normally less than 1%, it is predominantly deposited
in the compound middle lamella, and the tori of bordered pit-membranes of coniferous
species (
Hafren J. and Westermark U.: Nordic Pulp and Paper 16 (4), 284-290, 2001). The main component of pectin is polygalacturonan consisting of galacturonic acid
units that to various extend are esterified. When in free acid form, the carboxylic
groups of the galacturonan having a negative charge can induce local swelling of the
fibers in contact with aqueous solutions. The esterified groups, on the other hand,
can be de-esterified through for instance alkaline treatment and thus contributing
to swelling.
[0012] Given the technical background, the present invention is aimed to utilize the specific
features of pectin with respect to its specific location and the potential to induce
selective weakening in the fiber wall. Enzyme with specific activity towards pectin
is used for the pretreatment of cellulose fiber material. Maceration of the fiber
material prior to the enzyme treatment proves an efficient way to get the enzyme in
place. To render the fiber separation in the region where chemical weakening occurs,
the refining condition is optimized in respect to refining intensity and preheating
temperature. The results according to the present invention are a significantly reduced
refining energy to reach a given pulp freeness and improved strength and optical properties
of the pulp.
[0013] According to one aspect of the invention, the pretreatment is preferably assisted
by a mechanical compression to facilitate liquor uptake and to give a more even treatment
of the material. Compression screw device or twin roll presses can be used at a compression
ratio of 1:1 to 8:1. The pretreatment can be further improved if presteaming is conducted
prior to the compression.
[0014] Impregnation according to the invention follows immediately after the compression
and/or thermal pretreatment. The pectinase is charged in an amount required for sufficient
treatment, preferably 2,000,000 to 200,000,000 polygalacturonase units/ton material
and even more preferred 10,000,000 to 50,000,000 polygalacturonase units/ton. The
retention time of treatment is 3 min to 24 hours, preferably 3 to 300 min, even more
preferred 15 to 240 min and most preferred 30 to 120 min at a temperature of 20 to
100°C, preferably 35 to 70°C, and more preferably about 50°C. The treatment condition
can be adjusted depending on the charge of the pectinase to allow for a sufficient
hydrolysis of the pectins. Other pectinase preparations can be used provided that
the pectolytic activity is satisfied.
[0015] Defibration and refining of the pectinase treated material can be carried out either
at conventional TMP conditions and high intensity conditions. A surprising energy
reduction effect is obtained. To reach a given pulp freeness of 100 ml CSF, the energy
reduction is 400 kWh/t with TMP condition, from 2500 kWh/t without pectinase treatment
to 2100 kWh/t with pectinase treatment, or by about 16%. The energy reduction is 150
kWh/t with high intensity condition, from 2150 kWh/t without pectinase treatment to
2000 kWh/t with pectinase treatment, or by about 7%. The combination of high intensity
and pectinase treatment gives a total reduction of 500 kWh/t, from 2500 kWh/t to 2000
kWh/t at a pulp freeness of 100 ml CSF, which is 20% in reduction. The shives content
decreases more rapidly after the pectinase treatment.
[0016] The strength properties remain the same as compared to conventional TMP, and improved
by about 10% as compared to high intensity TMP. The brightness of the pulp is also
increased by the enzymatic treatment.
[0017] While the addition of DTPA or sulfite doesn't contribute to further energy reduction,
it increases the brightness by 2 to 5 brightness units. The improved brightness is
maintained after peroxide bleaching, together with the benefit of an increased amount
of residual peroxide for recycling.
[0018] The surprising effects resulting from the pectinase treatment could be explained
by a selective weakening of the pectin-enriched region in the fiber wall due to hydrolysis
of the pectins, with the consequence of a more efficient fiber separation in defibration
and refining of the material. It is evident to those skilled in the art that this
process can bring about a significant economical benefit, in terms of improved pulp
properties and reduced energy cost. It is also evident to those skilled in the art
that any enzyme preparation that contains sufficient pectolytic hydrolysis activity,
alone or in combination with other chemicals, can be used for the treatment according
to the present invention.
The present invention describes a mechanical pulping process comprising:
DETAILED DESCRIPTION OF THE INVENTION
[0019]
- A) Mechanical pretreatment of the comminuted fiber material with suitable mechanical
means, for instance compression with screw device or roll press device, to enable
an efficient uptake of aqueous solution into the fiber material during an impregnation
immediately following the pretreatment. Replacement of resin-containing liquor in
natural cellulose fiber material with added aqueous solution is also positive in a
process point of view. The compression ratio is preferably in the range of 1:1 to
8:1, preferably 2:1 to 5:1, where 1:1 means a screw conveyer transporting the fiber
material into the impregnation bin. In combination with compression treatment, an
initial thermal heating of the fiber material may further facilitate an efficient
uptake of the aqueous solution, preferably by use of fresh or recycled steam at atmospheric
pressure, for 1 to 30 min, preferably 10 to 20 min. As an alternative, thermal heating
followed immediately by impregnation may be used instead of compression treatment
when no such facility is available. The pretreatment procedure can also be repeated
in one to several stages with the freedom of applying various impregnation chemicals
in different stages.
- B) Impregnation of the fiber material with pectinase-containing aqueous liquid. Added
in connection with or immediately after the pretreatment stage, the enzyme can more
easily reach the sites of reaction. In addition to the pectinase enzyme, other chemicals
for instance chelating agents such as sulfite, preferably at a charge of 5 to 50 kg/ton,
and/or DTPA, preferably at a charge of 1 to 10 kg/ton, may be added in the impregnation
to further improve the process. The pectinase-containing liquid may comprise an enzymatic
preparation with pectolytic activity for both un-esterified pectins and esterified
pectins. Moreover, the aqueous liquid may comprise two or more enzymatic preparations
wherein at least one of the preparations has pectinase activity; or the pectinase
may be added as a biological agent comprising one or more fungi or bacteria, at least
one of which having pectolytic activity. The charge of enzyme is subject to process
conditions and cost effectiveness, and lies in the range of 2,000,000 to 200,000,000
polygalacturonase units/ton fiber material, preferably 10,000,000 to 50,000,000 polygalacturonase
units/ton. The pH of the impregnation liquor is adjusted by alkali or acid, preferably
by caustic soda or mineral acid, to a value optimal for enzymatic reactions, suitably
in the pH range of 3 to 10, preferably 4 to 7 and more preferably about 5. The retention
time and temperature are also adjusted depending on the process setup and reaction
requirements, preferably being 3 to 300 min at a temperature of 20 to 100°C. It is
evident to those skilled in the art that any enzyme that contains sufficient pectolytic
activity, alone or in combination with other chemicals, can be used in the treatment
as described.
- C) Defibration and refining of the impregnated fiber material is carried out under
optimized conditions. The fiber material is preferably preheated prior to feeding
into the pressurized primary refiner, to allow for thermal softening of the fiber
wall. The pulping conditions can comprise a refiner rotation speed of 1000 to 3000
rpm, preferably 1500 to 2600 rpm, using either conventional TMP or high refining intensity.
Conventional TMP conditions may comprise preheating at 0 and up to 4 or 5 bar with
a retention time of 2-10 min in the preheater and a refiner rotation speed of 1200
to 1800 rpm. The pressure 0 bar means atmospheric refining. High intensity conditions
may comprise preheating at above 4 or 5 bar and up to 8 bar with a retention time
of 3 to 30 sec and a refiner rotation speed above 2000 rpm but usually not above 3000
rpm. The retention time should be matched against the preheating temperature (steam
pressure) as high preheating temperature requires shorter retention time. After the
primary refining, a secondary refining stage can be used to reach the required pulp
freeness. The second-dary refining stage may have the same conditions as the primary
stage.
[0020] Although disc refiners are the defibration and refining equipment used in this study,
other mechanical devices can be used for the purpose of defibration and refining.
Some of the examples are conical refiners and stone ground wood grinders. The refiners
can be of the single disc or double disc type. The refining may be made in a single
stage or in multistage. The defibration and refining can also be done at atmospheric
pressure, in which case refiner mechanical pulping, or RMP is a more appropriate description
of the process instead of TMP.
[0021] Although only softwood fiber material is used in this study, any fiber material containing
pectins could be treated with this method. The fiber material could be hardwood fiber
material, non-wood fibers such as bagasse, bamboo, reed and straw.
[0022] The embodiment as described here can be modified according to the source of fiber
material and the process set-up.
[0023] The pulp obtained can depending on the application of the pulp be subject to further
treatment such as washing, screening, post-refining and bleaching according to conventional
processes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In the following, there will be given a few examples of preferred embodiments according
to the invention. The invention is however not limited to these examples. Reference
is made to the enclosed drawing diagrams, of which:
Fig. 1 is showing freeness vs. specific refining energy for Example 1,
Fig. 2 is showing freeness vs. specific refining energy for Example 2,
Fig. 3 is showing freeness vs. specific refining energy for Example 3.
EXAMPLES
[0025] Mechanical pulps are produced by different chemical treatments, in a pilot refiner
plant. The process conditions are as follows.
Material
[0026] Wood chips consisting of approximately one third white spruce, one third red and
black spruce and one third balsam fir, all of Canadian origin in the Nova Scotia region.
The chips are prepared with mill-size chipper and well mixed prior to the trials.
Pretreatment
[0027] The chips are pre-steamed at atmospheric pressure for 15 min. After pre-steaming
the chips are fed into a plug-screw device with a compression ratio of 4:1. At the
outlet of the device, the chips are released into a solution containing various chemicals,
including pectinase in the trials according to the invention. The pH of the solution
is kept at about 5 adjusted by use of sodium hydroxide or sulfuric acid.
Impregnation and retention
[0028] After passing through the impregnation bin, the chips are stored in well-isolated
barrels. The retention time is 120 min at a temperature around 50°C. The pectinase
used in this study is a highly pectolytic enzyme preparation. This enzyme also hydrolyzes
the methyl-esterified galacturonic acid in the pectins. The pectinase used is generated
by submerged fermentation of a group of microorganisms containing
Aspergillus aculeatus and
Aspergillus oryzae. The charge of pectinase in this study is 30,800,000 polygalacturonase units/ton.
The charges of DTPA and sodium sulfite are 4 kg/t and 12 kg/t, respectively, were
applicable.
Defibration and refining
[0029] The primary refiner is of the Sprout-Bauer 36-1 CP single disc refiner type. Two
pulping conditions, conventional TMP and high intensity HI-TMP, are applied. The preheating
steam pressure is 2.8 bar for TMP and 5.9 bar for high intensity (HI-TMP). The retention
time at preheating is 3.4 min for TMP and 12 sec for HI-TMP. The refiner rotation
speed is 1800 rpm for TMP and 2600 rpm for HI-TMP. The secondary refining is carried
out with a double disc atmospheric refiner to reach the final freeness levels.
[0030] The obtained pulps are evaluated both for strength properties and optical properties
including a bleachability study with hydrogen peroxide bleaching.
EXAMPLE 1
[0031] In this trial TMP conditions are applied for both samples with the difference that
reference, Sample 1, is impregnated only with water adjusted to pH 5.
[0032] Sample 1: TMP condition with only water impregnation with pH adjusted to 5.
[0033] Sample 2: TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
[0034] It is shown in Table 1 that the specific energy consumption required to reach a given
freeness is significantly reduced by the enzymatic treatment. The degree of reduction
is approximately 400 kWh/t at a given freeness, which also can be seen in Figure 1.
The pulp properties for those samples are comparable to each other over the freeness
range applicable for paper manufacture. The shives content is more rapidly reduced
by the pectinase treatment. At a freeness of 57 ml CSF, the shives content is 0.12%
as compared to the reference, 0.34%.
Table 1.
| |
Sample 1 |
Sample 2 |
| Freeness, ml CSF |
665 |
230 |
148 |
129 |
57 |
656 |
115 |
57 |
36 |
| |
|
|
|
|
|
|
|
|
|
| SEC (kWh/t) |
902 |
1889 |
2028 |
2237 |
3078 |
824 |
1993 |
2386 |
3000 |
| Density (kg/m3) |
|
309,6 |
344,83 |
371,75 |
440,53 |
205,76 |
384,62 |
446,43 |
462,96 |
| Bulk (cm3/g) |
|
3,23 |
2,9 |
2,69 |
2,27 |
4,86 |
2,6 |
2,24 |
2,16 |
| Burst ind. (kPam2/g) |
|
1,65 |
1,98 |
2,29 |
3,04 |
0,34 |
2,46 |
3,1 |
3,35 |
| Tear ind. (mNm2/g) |
|
10,9 |
9,6 |
9,5 |
7,9 |
4,8 |
8,7 |
8 |
7,4 |
| Tens ind. (N.m/g) |
|
33,9 |
39,9 |
42,7 |
53,5 |
10,1 |
42,9 |
55,5 |
57,4 |
| %Stretch |
|
2,03 |
2 |
2,08 |
2,57 |
1,1 |
2,2 |
2,5 |
2,67 |
| T.E.A.(J/m2) |
|
28,48 |
32,7 |
36,95 |
57,6 |
4,6 |
39,7 |
28,6 |
64,3 |
| |
|
|
|
|
|
|
|
|
|
| %Opacity |
|
97 |
97 |
97,4 |
98,4 |
88,2 |
98,1 |
97,5 |
97,5 |
| Light scatt. coe.(m2/kg) |
|
50,1 |
52,1 |
52,8 |
61,4 |
35,3 |
53,9 |
59,2 |
65,1 |
| ISO% |
44,5 |
48,8 |
48,6 |
49,8 |
62,3 |
46,6 |
50 |
52,6 |
52,2 |
| |
|
|
|
|
|
|
|
|
|
| %shives(Pulmac-0.1mm) |
15 |
1,3 |
0,98 |
0,8 |
0,34 |
13,9 |
0,6 |
0,12 |
0,05 |
EXAMPLE 2
[0035] In this trial the high intensity condition is applied for both samples with the difference
that the reference, Sample 3, is impregnated only with water adjusted to pH 5.
[0036] Sample 3: HI-TMP condition with only water in the impregnation adjusted to pH 5.
[0037] Sample 4: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH
5.
Table 2.
| |
Sample 3 |
Sample 4 |
| Freeness, ml CSF |
714 |
293 |
197 |
126 |
54 |
725 |
254 |
236 |
121 |
72 |
| SEC (kWh/t) |
531 |
1482 |
1652 |
1897 |
2655 |
412 |
1362 |
1462 |
1793 |
2344 |
| |
|
|
|
|
|
|
|
|
|
|
| Density(kg/m3) |
|
311,53 |
362,32 |
389,11 |
454,55 |
|
317,46 |
321,54 |
387,6 |
423,73 |
| Bulk (cm3/g) |
|
3,21 |
2,76 |
2,57 |
2,2 |
|
3,15 |
3,11 |
2,58 |
2,36 |
| Burst ind. (kPa.m2/g) |
|
1,47 |
1,78 |
2,07 |
2,96 |
|
1,82 |
1,85 |
2,6 |
3,2 |
| Tearind. (mNm2/g) |
|
10,1 |
8,3 |
8,5 |
7,7 |
|
11,1 |
11,1 |
9,4 |
9,2 |
| Tens ind. (N.m/g) |
|
30,2 |
34,9 |
40,8 |
51,6 |
|
34,7 |
35,4 |
47,3 |
53,3 |
| %Stretch |
|
1,97 |
2,08 |
2,03 |
2,63 |
|
2 |
2,1 |
2,5 |
2,54 |
| T.EA.(J/m2) |
|
24,73 |
29,74 |
35,27 |
58,53 |
|
30,1 |
32,4 |
49,3 |
57,3 |
| |
|
|
|
|
|
|
|
|
|
|
| %Opacity |
|
94,6 |
95,4 |
96,7 |
97,2 |
|
95,3 |
94,8 |
96,6 |
97,1 |
| Light scatt.coe.(m2/kg) |
|
41,2 |
49,3 |
61,6 |
62,6 |
|
49,4 |
48,9 |
59,3 |
60,8 |
| ISO% |
45,3 |
50,3 |
50,1 |
52 |
53,9 |
44,8 |
50,6 |
50,8 |
51,6 |
54,4 |
| |
|
|
|
|
|
|
|
|
|
|
| %shives(Pulmac-0.1mm) |
8,42 |
0,62 |
0,5 |
0,38 |
0,04 |
8,76 |
0,52 |
0,4 |
0,14 |
0,06 |
[0038] It is shown in Table 2 and Figure 2 that the enzymatic treatment has a surprising
effect on energy reduction also with the high intensity condition. To reach a given
freeness of down to about 100 ml CSF, the specific energy consumption is reduced by
about 150 kWh/t. The reduction is less pronounced at lower freeness. The pulp properties
at the same time are improved by about 10% both for tensile strength and tear strength,
while the optical properties remain at the same level. The potential of the enzymatic
treatment makes is obvious to people skilled in the art that even better strength
can be achieved if the same amount of energy is applied to the enzymatically treated
pulps, or even less energy is required if the same strength properties are to be acquired.
EXAMPLE 3
[0039] In this trial the HI-TMP condition is applied for all the samples with Sample 3 and
Sample 4 from Example 2 as references.
[0040] Sample 3: HI-TMP condition with only water in the impregnation adjusted to pH 5.
[0041] Sample 4: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH
5.
[0042] Sample 5: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4
kg/t DTPA, pH 5.
[0043] Sample 6: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4
kg/t DTPA and 12 kg/t sodium sulfite, pH 5.
Table 3
| |
Sample 3 |
Sample 4 |
Sample 5 |
Sample 6 |
| Freeness, ml CSF |
293 |
197 |
126 |
54 |
254 |
236 |
121 |
72 |
201 |
148 |
87 |
52 |
184 |
150 |
97 |
55 |
| SEC (kWh/t) |
1482 |
1652 |
1897 |
2655 |
1362 |
1462 |
1793 |
2344 |
1539 |
1681 |
2022 |
2676 |
1934 |
2082 |
2303 |
3040 |
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Density (kg/m3) |
311,53 |
362,32 |
389,11 |
454,55 |
317,46 |
321,54 |
387,6 |
423,73 |
340,14 |
362,32 |
413,22 |
446,43 |
384,62 |
358,42 |
398,41 |
436,68 |
| Bulk (cm3/g) |
3,21 |
2,76 |
2,57 |
2,2 |
3,15 |
3,11 |
2,58 |
2,36 |
2,94 |
2,76 |
2,42 |
2,24 |
2,6 |
2,79 |
2,51 |
2,29 |
| Burst ind. (kPa.m2/g) |
1,47 |
1,78 |
2,07 |
2,96 |
1,82 |
1,85 |
2,6 |
3,2 |
1,87 |
2 |
2,63 |
3,1 |
2,3 |
2,24 |
2,61 |
3 |
| Tear ind. (mNm2/g) |
10,1 |
8,3 |
8,5 |
7,7 |
11,1 |
11,1 |
9,4 |
9,2 |
8,6 |
8,8 |
8,5 |
7,8 |
9,8 |
9,5 |
10,3 |
7,4 |
| Tens ind. (N.m/g) |
30,2 |
34,9 |
40,8 |
51,6 |
34,7 |
35,4 |
47,3 |
53,3 |
37,1 |
41,3 |
47,1 |
52,8 |
41,7 |
41,3 |
47,1 |
51,1 |
| %Stretch |
1,97 |
2,08 |
2,03 |
2,63 |
2 |
2,1 |
2,5 |
2,54 |
2,2 |
2,1 |
2,56 |
2,7 |
2,1 |
2,5 |
2,6 |
2,9 |
| T.E.A.(J/m2) |
24,73 |
29,74 |
35,27 |
58,53 |
30,1 |
32,4 |
49,3 |
57,3 |
33 |
37,9 |
48,3 |
57 |
35,2 |
40,1 |
47,2 |
56,6 |
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| %Opacity |
94,6 |
95,4 |
96,7 |
97,2 |
95,3 |
94,8 |
96,6 |
97,1 |
94,1 |
95,4 |
96 |
96,6 |
93,2 |
94,2 |
95,2 |
95,5 |
| Light scatt.coe.(m2/kg) |
41,2 |
49,3 |
61,6 |
62,6 |
49,4 |
48,9 |
59,3 |
60,8 |
52,5 |
55,6 |
58,2 |
60,2 |
49,3 |
53,6 |
57,8 |
60,1 |
| ISO% |
50,3 |
50,1 |
52 |
53,9 |
50,6 |
50,8 |
51,6 |
54,4 |
52,1 |
52,9 |
54 |
56 |
55,4 |
55,8 |
56,3 |
58,8 |
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| %shives(Pulmac-0.1mm) |
0,62 |
0,5 |
0,38 |
0,04 |
0,52 |
0,4 |
0,14 |
0,06 |
0,68 |
0,54 |
0,3 |
0,07 |
1 |
0,68 |
0,48 |
0,09 |
[0044] The refining energy consumption, SEC, is not affected by additional charge of DTPA
or DTPA/sulfite. The SEC is at the same level for all samples with pectinase treatment,
about 150 kWh/t lower compared to Sample 3, i.e. high intensity condition without
pectinase treatment, also see Figure 3. A surprising effect is however obtained in
the brightness of unbleached pulp. With DTPA together with pectinase, the brightness
is increased by about 2 units ISO. With a combined of pectinase, DTPA and sulfite,
the brightness improvement is even higher, 4-5 units ISO. The brightness improvement
is fairly constant in the entire freeness range.
EXAMPLE 4
[0045] Pulps with different treatments are bleached with alkaline peroxide with following
bleach conditions:
- Pretreatment with 7 kg DTPA/t at 7% consistency, 90°C, pH 5 for 45 min before dewatering
to 30%.
- Bleaching at 25% consistency at 30kg/t hydrogen peroxide charge, 80°C for 90 min.
Three sodium hydroxide charges, 10, 20 and 30kg/t, are used to find the optimal brightness.
The optimal brightness and corresponding residual peroxide are given as bleach results.
[0046] Sample 7: TMP condition with only water impregnation with pH adjusted to 5.
[0047] Sample 8: TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
[0048] Sample 9: HI-TMP condition with only water in the impregnation adjusted to pH 5.
[0049] Sample 10: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase,
pH 5.
[0050] Sample 11: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase,
4 kg/t DTPA, pH 5.
[0051] Sample 12: HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase,
4 kg/t DTPA and 12 kg/t sodium sulfite, pH 5.
Table 4
| |
Unbl. ISO% |
Bleached ISO% |
Res. H2O2 % |
| Sample 7 |
52,3 |
68,1 |
7,5 |
| Sample 8 |
54,7 |
70,6 |
16,8 |
| Sample 9 |
53,9 |
68,3 |
5,6 |
| Sample 10 |
54,4 |
71,9 |
19,9 |
| Sample 11 |
56.0 |
71,4 |
12,9 |
| Sample 12 |
59,5 |
74,3 |
25,3 |
[0052] It is shown in Table 4 that the brightness improvement is maintained after the enzymatic
treatment. The improvement is about 2.5 brightness units for the TMP condition, and
3.6 units for the HI-TMP condition. Combination of DTPA and sulfite in the impregnation
gives further improvement to a brightness of 74.3%ISO, compared to the TMP reference
of 68.1%ISO.
[0053] Noticeably, the residual peroxide is much higher with the enzymatically treated samples.
This is beneficial because the residual chemicals are recycled back to the process
after bleaching. The need of make-up peroxide is reduced accordingly.
[0054] The invention is not limited by the embodiments described above, but may be varied
within the scope of the claims.
1. A method of producing mechanical pulp wherein, for reducing refining energy consumption
while improving optical and strength properties of the produced mechanical pulp, the
method comprises the steps of:
a) initially compressing a fiber material;
b) selectively weakening a pectin-enriched region in the fiber walls of the fiber
material by impregnating the fiber material with a pectinase-containing aqueous liquid,
resulting in hydrolysis of the pectins;
c) defibrating and refining the fiber material to produce a mechanical pulp.
2. A method according to claim 1, characterised in that said initial compression of the fiber material is a mechanical compression, preferably
combined with a thermal pretreatment of the fiber material, preferably by steaming,
before the impregnation.
3. A method according to claim 2, characterised in that steaming is carried out, preferably at atmospheric pressure, for 1 to 30 min, preferably
10 to 20 min.
4. A method according to claim 2 or 3, characterised in that compression is performed by a compression screw or a twin roll press, with a compression
ratio of 1:1 to 8:1, preferably 2:1 to 5:1.
5. A method according to anyone of the preceding claims, characterised in that the pectinase-containing liquid comprises an enzymatic preparation with pectolytic
activity for both pectins and esterified pectins.
6. A method according to anyone of the preceding claims, characterised in that the aqueous liquid comprises two or more enzymatic preparations wherein at least
one of the preparations has pectinase activity.
7. A method according to anyone of claims 1-5, characterised in that the pectinase is added as a biological agent comprising one or more fungi or bacteria,
at least one of which having pectolytic activity.
8. A method according to anyone of the preceding claims, characterised in that the pectinase arises from a group of microorganisms containing Aspergillus aculeatus and Aspergillus oryzae.
9. A method according to anyone of the preceding claims, characterised in that the charge of pectinase is 2,000,000 to 200,000,000 polygalacturonase units/ton fiber
material, preferably 10,000,000 to 50,000,000 polygalacturonase units/ton.
10. A method according to anyone of the preceding claims, characterised in that the aqueous liquid comprises at least one chelating agent, preferably diethylenetetraminepentaacetic
acid at a charge of 1 to 10 kg/ton and/or sulfite at a charge of 5 to 50 kg/ton.
11. A method according to anyone of the preceding claims, characterised in that a retention time after uptake of the impregnation liquid is 3 min to 24 hours, preferably
15 to 240 min, and more preferably 30 to 120 min.
12. A method according to claim 11, characterised in that a temperature in the retention after uptake of the impregnation liquid is 20 to 100°C,
preferably 35 to 70°C, and more preferably about 50°C.
13. A method according to anyone of the preceding claims, characterised in that a pH in the impregnation liquid is 3 to 10, preferably 4 to 7, and more preferably
about 5.
14. A method according to anyone of the preceding claims, characterised in that the defibration and refining of the fiber material is performed by use of single
disc, double disc or conical refiners in one or multi stages.
15. A method according to claim 14, characterised in that a refiner rotation speed is 1000 to 3000 rpm, preferably 1500 to 2600 rpm.
16. A method according to claim 14, characterised in that the fiber material is preheated for 2 to 10 min before refining, that a refiner pressure
is from atmospheric up to 5 bar, preferably up to 4 bar and that a refiner rotation
speed preferably is 1200 to 1800 rpm.
17. A method according to claim 14, characterised in that the fiber material is preheated for 3 to 30 sec before refining, that a refiner pressure
is from 4 to 8 bar, preferably 5 to 8 bar and that a refiner rotation speed preferably
is above 2000 rpm.
18. A method according to anyone of the preceding claims, characterised in that said fiber material is softwood chips or hardwood chips.
19. A method according to anyone of claims 1-17, characterised in that the fiber material is non-wood fiber material including bagasse, bamboo, reed and
straw.
20. A method according to anyone of the preceding claims, characterised in that the pulp obtained after defibration and refining is bleached, preferably with alkaline
peroxide, to obtain bleached pulp having high brightness.
21. Mechanical pulp, characterised in that it has been produced by a method according to any one of claims 1-20.
1. Verfahren zur Herstellung von Holzstoff, bei welchem zur Verringerung des Energieverbrauchs
bei der Mahlung unter Verbesserung der optischen Eigenschaften und des Festigkeitsverhaltens
des so hergestellten Holzstoffs das Verfahren die folgenden Schritte umfasst:
a) anfängliches Verdichten eines Fasermaterials;
b) selektive Verringerung der Festigkeit eines mit Pektin angereicherten Bereichs
in den Faserwänden des Fasermaterials durch Imprägnieren des Fasermaterials mit einer
Pektinase enthaltenden wässrigen Flüssigkeit, was zur Hydrolyse der Pektine führt;
c) Zerfasern und Mahlen des Fasermaterials zur Bildung eines Holzstoffs.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass es sich bei der anfänglichen Verdichtung des Fasermaterials um eine mechanische Verdichtung
handelt, vorzugsweise in Verbindung mit einer Wärme-Vorbehandlung des Fasermaterials,
vorzugsweise durch Dampfbehandlung, vor der Imprägnierung.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Dampfbehandlung vorzugsweise bei atmosphärischem Druck 1 bis 30 Minuten lang,
vorzugsweise 10 bis 20 Minuten lang, durchgeführt wird.
4. Verfahren nach Anspruch 2 oder 3, dadurch gekennzeichnet, dass die Verdichtung mittels einer Quetschschraube oder einer Doppelwalzenpresse mit einem
Verdichtungsverhältnis von 1:1 bis 8:1, vorzugsweise von 2:1 bis 5:1, vorgenommen
wird.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Pektinase enthaltende Flüssigkeit ein Enzympräparat mit pektolytischer Wirkung
sowohl auf Pektine als auch veresterter Pektine enthält.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die wässrige Flüssigkeit zwei oder mehr Enzympräparate enthält, wobei mindestens
eines der Präparate eine Pektinasewirkung entfaltet.
7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Pektinase als biologischer Wirkstoff zugesetzt wird, welcher einen oder mehrere
Pilze oder Bakterien enthält, von denen einer bzw. eines eine pektolytische Wirkung
besitzt.
8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Pektinase aus einer Gruppe von Mikroorganismen stammt, welche Aspergillus aculeatus und Aspergillus oryzae enthält.
9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Einsatz an Pektinase 2.000.000 bis 200.000.000 Polygalakturonase-Einheiten pro
Tonne Fasermaterial, vorzugsweise 10.000.000 bis 50.000.000 Polygalakturonase-Einheiten/Tonne,
beträgt.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die wässrige Flüssigkeit mindestens ein Mittel zur Chelatbildung enthält, vorzugsweise
Diethylen-Tetramin-Pentaessigsäure in einer Einsatzmenge von 1 bis 10 kg/Tonne und/oder
Sulfit in einer Einsatzmenge von 5 bis 50 kg/Tonne.
11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass nach dem Aufnehmen der Imprägnierflüssigkeit eine Verweildauer von 3 Minuten bis
24 Stunden, vorzugsweise 15 bis 240 Minuten und besonders bevorzugter Weise von 30
bis 120 Minuten vorgesehen ist.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass die Temperatur während der Verweildauer nach dem Aufnehmen der Imprägnierflüssigkeit
20 bis 100 °C, vorzugsweise 35 bis 70 °C und besonders bevorzugter Weise etwa 50 °C
beträgt.
13. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der pH-Wert in der Imprägnierflüssigkeit 3 bis 10 beträgt, vorzugsweise 4 bis 7 und
besonders bevorzugter Weise etwa 5.
14. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Zerfasern und Mahlen des Fasermaterials unter Verwendung eines Einscheiben-,
Doppelscheiben- oder konischen Refiners in einer oder mehreren Stufen vorgenommen
wird.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Umlaufgeschwindigkeit des Refiners 1.000 bis 3.000 UpM, vorzugsweise 1.500 bis
2.600 UpM, beträgt.
16. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass das Fasermaterial 2 bis 10 Minuten lang vor der Mahlung vorgewärmt wird, dass der
Druck im Refiner vom atmosphärischen Druck bis zu 5 bar, vorzugsweise bis zu 4 bar,
beträgt und dass die Umlaufgeschwindigkeit des Refiners vorzugsweise 1.200 bis 1.800
UpM beträgt.
17. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass das Fasermaterial 3 bis 30 Sekunden lang vor der Mahlung vorgewärmt wird, dass der
Druck im Refiner von 4 bis 8 bar beträgt, vorzugsweise von 5 bis 8 bar, und dass die
Umlaufgeschwindigkeit des Refiners vorzugsweise über 2.000 UpM liegt.
18. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Fasermaterial aus Nadelholzspänen oder Hartholzspänen besteht.
19. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass das Fasermaterial aus anderem Fasermaterial als Holzspänen besteht, das Zuckerrohr,
Bambus, Schilfrohr und Stroh umfasst.
20. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der nach Zerfaserung und Mahlung erhaltene Holzstoff gebleicht wird, vorzugsweise
mit einem basischen Peroxid, um so einen gebleichten Holzstoff von hoher Helligkeit
zu erhalten.
21. Holzstoff. dadurch gekennzeichnet, dass er mit einem Verfahren nach einem der Ansprüche 1 bis 20 hergestellt ist.
1. Procédé pour la production d'une pâte à papier mécanique, dans lequel, pour réduire
la consommation d'énergie de raffinage tout en améliorant les propriétés optiques
et de résistance mécanique de la pâte mécanique produite, le procédé comprend les
étapes consistant à :
a) comprimer initialement une matière en fibres ;
b) affaiblir sélectivement une région enrichie en pectine dans les parois des fibres
de la matière en fibres en imprégnant la matière en fibres avec un liquide aqueux
contenant une pectinase, avec pour résultat l'hydrolyse des pectines ;
c) défibrer et raffiner la matière en fibres pour produire une pâte mécanique.
2. Procédé suivant la revendication 1, caractérisé en ce que ladite compression initiale de la matière en fibres est une compression mécanique,
de préférence combinée avec un prétraitement thermique de la matière en fibres, de
préférence par étuvage, avant l'imprégnation.
3. Procédé suivant la revendication 2, caractérisé en ce que l'étuvage est effectué, de préférence à la pression atmosphérique, pendant 1 à 30
min, de préférence 10 à 20 min.
4. Procédé suivant la revendication 2 ou 3, caractérisé en ce que la compression est effectuée par une vis de compression ou une presse à deux cylindres,
avec un rapport de compression de 1:1 à 8:1, de préférence de 2:1 à 5:1.
5. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le liquide contenant une pectinase comprend une préparation enzymatique ayant une
activité pectolytique à la fois pour les pectines et les pectines estérifiées.
6. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le liquide aqueux comprend deux ou plus de deux préparations enzymatiques, au moins
une des préparations ayant une activité de pectinase.
7. Procédé suivant l'une quelconque des revendications 1 à 5, caractérisé en ce que la pectinase est ajoutée comme agent biologique comprenant un ou plusieurs champignons
ou une ou plusieurs bactéries, dont au moins l'un a une activité pectolytique.
8. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que la pectinase est issue d'un groupe de micro-organismes contenant Aspergillus aculeatus et Aspergillus oryzae.
9. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que la charge de pectinase est de 2 000 000 à 200 000 000 d'unités de polygalacturonase/
tonne de matière en fibres, de préférence de 10 000 000 à 50 000 000 d'unités de polygalacturonase/tonne.
10. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le liquide aqueux comprend au moins un agent chélatant, de préférence l'acide diéthylène-tétraminepentaacétique
en une charge de 1 à 10 kg/tonne et/ou un sulfite en une charge de 5 à 50 kg/tonne.
11. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'un temps de rétention, après absorption du liquide d'imprégnation, va de 3 min à 24
heures, avantageusement de 15 à 240 min, et plus avantageusement de 30 à 120 min.
12. Procédé suivant la revendication 11, caractérisé en ce qu'une température dans la rétention après absorption du liquide d'imprégnation est de
20 à 100°C, avantageusement de 35 à 70°C et plus avantageusement égale à environ 50°C.
13. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'un pH dans le liquide d'imprégnation est de 3 à 10, avantageusement de 4 à 7 et plus
avantageusement égal à environ 5.
14. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le défibrage et le raffinage de la matière de fibres sont effectués en utilisant
des raffineurs à un disque, à deux disques ou coniques dans une ou plusieurs étapes.
15. Procédé suivant la revendication 14, caractérisé en ce qu'une vitesse de rotation du raffineur est de 1000 à 3000 tr/min, de préférence de 1500
à 2600 tr/min.
16. Procédé suivant la revendication 14, caractérisé en ce que la matière en fibres est préchauffée pendant 2 à 10 min avant raffinage, qu'une pression
du raffineur va de la pression atmosphérique jusqu'à 5 bars, de préférence jusqu'à
4 bars, et qu'une vitesse de rotation du raffineur est de préférence de 1200 à 1800
tr/min.
17. Procédé suivant la revendication 14, caractérisé en ce que la matière en fibres est préchauffée pendant 3 à 30 secondes avant raffinage, qu'une
pression du raffineur va de 4 à 8 bars, de préférence de 5 à 8 bars, et qu'une vitesse
de rotation du raffineur est de préférence supérieure à 2000 tr/min.
18. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que ladite matière en fibres consiste en copeaux de bois résineux ou copeaux de bois
de feuillus.
19. Procédé suivant l'une quelconque des revendications 1 à 17, caractérisé en ce que la matière en fibres est une matière en fibres, ne consistant pas en fibres de bois,
comprenant la bagasse, le bambou, le roseau et la paille.
20. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que la pâte obtenue après défibrage et raffinage est blanchie, de préférence avec un
peroxyde alcalin, pour obtenir une pâte blanchie ayant une grande brillance.
21. Pâte mécanique, caractérisée en ce qu'elle a été produite par un procédé selon l'une quelconque des revendications 1 à 20.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only.
It does not form part of the European patent document. Even though great care has
been taken in compiling the references, errors or omissions cannot be excluded and
the EPO disclaims all liability in this regard.
Patent documents cited in the description
Non-patent literature cited in the description
- HAFREN J.WESTERMARK U.Nordic Pulp and Paper, 2001, vol. 16, 4284-290 [0011]