• 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:
    According to the process, an enzyme preparation containing cellulases and/or hemicellulases is reacted with a homogeneous aqueous suspension of the papermaking pulp exhibiting a Schopper-Riegler (SR) value determined in accordance with NFQ standard 50 003 of at least 25. …<??>Application of the process for the treatment of a papermaking pulp based on recycled fibres.
    公开号:SU1701117A3
    申请号:SU874203419
    申请日:1987-09-21
    公开日:1991-12-23
    发明作者:Фюнтес Жан-Люк；Робер Мишель
    申请人:Ла Селлюлоз Дю Пэн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the pulp and paper industry, in particular to the production of paper.
    The aim of the invention is to intensify the process while maintaining the mechanical strength of the paper.
    According to the method of dewatering paper pulp, which includes treating it with a chemical reagent and pouring a paper web, an enzyme preparation containing cellulases and / or hemicellulases from cultures of Trichoderma viridae or Aspergillus niger microorganisms is used in the amount of 0.01-2.0% of the weight of dry fiber, while the enzyme preparation is introduced into the pulp with a degree of grinding equal to or higher than 25 ° SR.
    Paper industry is increasingly using recycled paper. For example, for the manufacture of corrugated cardboard, it is increasingly being resorted to using raw materials based on
    recycling fibers and in parallel increase the number of recycling. With each recycling, the quality of the raw materials deteriorates. To achieve a satisfactory level of mechanical properties, masses are usually refined in an aqueous suspension, which leads to mechanization difficulties.
    Masses in aqueous suspension ready for use in a paper machine can have different parameters, one of which is particularly important for determining the ability of the mass to remove water. For example, define X
    ABOUT
    H
     GO
    Dus Shopper-Riegler (SR) pulp as part of the evaluation of pulp quality for paper making. It expresses the ability of water to separate from the suspension under the conditions defined by the standard NFQ 50 003. On a scale from 0 to 100, the increased salinity of SR is expressed in a low rate of water removal from the suspension, while a small value is expressed in a higher water removal rates. For example, the mass subjected to the refining operation has a more or less elevated SR, depending on the degree of refining carried out, compared to the mass that has not been refined or poorly refined.
    This parameter is important for the productivity of the paper machine, since it is necessary for the water removal stage to take as little time as possible. For suspensions with an increased HR, it is necessary to increase the mass concentration in order to maintain the same production speed. This leads to worse sheet formation, since fibers are more difficult to distribute. Therefore, it is especially important to have suspensions with a sufficiently small SR.
    If the suspensions have an SR above 25, they will try to lower it to improve the paper making conditions. Such a reduction is desirable in two aspects: it is possible to increase the productivity of the paper machine by accelerating the removal of water; production speed can be maintained without the need to compensate for and slow water removal by reducing the suspension less, with the danger that this results in poor sheet formation.
    The proposed method is accepted not for unrefined paper masses, but for masses that already have an increased HR. The increased SHR value can be the result of a preliminary mechanical refining, which made the mass of good-quality paper with good mechanical properties, due to the fact that the mass has already undergone several recirculations, the result of combining two operations.
    A paper pulp having an LJP of 25, measured as a mass in a homogeneous suspension at 2 g / l under the conditions of the standard NFQ 50 003, is affected by an enzymatic composition containing cellulase and / or temicellulase. This treatment allows reducing the SR of the treated mass, not It has no undesirable effect on the mechanical properties of paper made from this mass.
    Processed paper pulps can be designed for the most varied
    paper applications. These are masses based on recycled fibers or unbleached or bleached chemical masses for making kraft paper. Mechanical masses such as masses used to make newsprint can also be called.
    Among all enzymatic formulations containing cellulases and / or hemcellcellulases, those that have Ci activity, Cx activity and xylanase activity are preferably chosen. Without accurate knowledge of the role of each of these activities, it may appear that the combination of the three activities leads to finding the desired effect. These three activities are determined by the international nomenclature of enzymes and they can be qualified and expressed in units of the international system (US1) in milligrams of powder of the enzymatic composition under consideration. The Ci activity is the action of cellobiohydrolase, which can be dosed in pure cellulose. This activity is manifested by
    0 cellobiase and in the international system means the AVICEL substrate as a control substrate. Cx activity is dosed on altered cellulase, carboxymethylcellulase, and it is quantitatively determined by a decrease in the viscosity of carboxylmethylcellulase or by an increase in reducing activities. Xylanase activity allows the hydrolysis of connective xylans.
    0 Advantageously, the treatment with enzymatic composition lasts no more than 60 minutes, since after this duration, SR has a tendency to increase slightly, remaining clearly lower than the original SR.
    5 The enzymatic composition is used at an enzyme concentration that varies depending on the activities of Ci, Cx, or on the xylanase activity of the enzymes contained in the composition. For example, the enzyme composition preferably has a concentration of from 0.01 to 2% by weight of dry weight, and these percentages correspond to a composition having a Ci activity of about 0.168 USI / mg powder,
    5 Cx activity in the order of 3.9 USI / mg powder and xylanase activity in the order of 31 USf / mg powder /
    The concentration of enzyme formulations should be adjusted depending on the type of composition used. None
    less at a concentration of about 0.01% by weight of the dry mass, no apparent effect is observed, except for prolonging the reaction time. At a concentration of more than 2% dry mass, the cost of the operation tends to increase excessively, and the mechanical properties of the manufactured paper tend to deteriorate.
    The reaction medium may be more or less suitable for the action of the enzymes, in particular the suitable temperature and pH conditions are conditions that eliminate the danger of the enzymes denaturing the medium. For example, the pH is preferably 3-7 and the temperature is 20-60 ° C. Above 60 ° C, the medium tends to denature the enzyme, and below 20 ° C, the effect of the enzymes is particularly slow.
    The proposed method can be used when the masses are used in a suspension based on recycle fibers. The processing makes it possible to markedly increase the productivity of the paper machine. Conventional mechanical refining is carried out before enzymatic treatment. Under these conditions, the mechanical properties of the paper produced, in particular, the rupture index or CMT, also increase.
    For all the masses that lead to the formation of paper, the mechanical properties of which are recognized as insufficient, they are impregnated with starch after the sheets are formed and dried on a paper machine. Under these conditions, not only a reduction in SR is obtained due to the enzomatic processing, but also an increase in mechanical properties, such as an indicator of rupture or SMT, by penetration with starch,
    After enzymatic treatment, the pulp mass is used on a conventional paper machine, which contains a table piece, equipped with a drawer that feeds the mass jets in an aqueous suspension to form a single-layer paper sheet, while the table portion is covered with a sheet to remove water from the mass and has a pressure section, section drying and starch impregnation device.
    The degree is determined by RR according to the NFQ 50 003 standard (measured as a mass in a homogeneous suspension at 2 g / l), the rupture index according to the NFQ 03 053 standard is quantified by the partial separation of the maximum pressure, uniformly distributed on the paper sample, perpendicular to its surface, on paper weight in grams. SMT
    (Corrugated medium test) - shows the compressive strength of corrugated paper and represents the degree of compression on the edge. The test is carried out as follows: the paper is compressed after holding for 60 minutes.
    Pnn (kg) x 100 Pochazetel SMToo -,
    (weight) (g / m)
    Example 1. Preparation of an aqueous suspension of paper pulp based on recycled fibers.
    Weigh 5 kg of the dry mass formed from 40% of fibers obtained from regenerated cardboard boxes (CCR) (M from 60% of fibers obtained from non-standard from the warehouse) and put the mass into the reactor. The aqueous suspension is made at 3.5% by weight by adding water to a total mass of 143 kg. Adjust the slit pI to 4.8 by adding 900 cm 1 H.H2S04, rotate the reactor at 50 rpm to homogenize the suspension. Preheat the reactor for 90 minutes to 60 ° C, then enter t 0.1 wt.% with respect to the mass of the dry mass of the enzymes obtained as follows: take 5 g of powder Maxazyme CL 2000, marketed by the company Rapidase (RAPIDASE). The product differs in that it originates from a culture of the microorganism Trichoderma vitidae and has a Ci activity of about 0.168 units of the international system, CX activity of about 3.91 units of international system , xylanase activity of about 31 units of the international system and FPU (Filter paper unit) on the order of 0.28. This powder is placed in 2800 g of water adjusted to pH 4.8 and the aqueous solution of enzymes thus obtained is introduced into the reactor. The reaction is carried out maxima for 30 minutes.
    Stop the reaction by diluting the contents of the reactor until a suspension of 7 g / l is obtained.
    FP is measured in the framework of the example immediately before the introduction of the enzymes and 30 minutes after the introduction of the enzymes. Its value varies from 54 to 44.
    Under identical conditions, a control suspension is prepared at the same time, which is not treated with an enzymatic solution, and the suspension is fed to an experimental papermaking machine to form a single-layer sheet with a mass of 120 g / m.
    Note the following mechanical properties:
    Test Example 1
    sample Gap indicator 1,831,84
    CMT129124
    Note that the treatment does not destroy the mechanical properties.
    Example 2. The conditions of example 1 are repeated, except that prior to the introduction of enzymes, the suspension mass is mechanically refined using a SPROUT-WALDRON refiner to obtain SR of about 74. 30 minutes after the introduction of enzymes, SR decreases to 59.
    Note the following mechanical properties:
    Test Example 2
    sample Gap indicator 1,832,07
    CMT129141
    Consequently, a marked improvement in mechanical properties is noted, while the negative effects of mechanical refining on the amount of SR, For the final SR (59), which is approximately identical to the original SR (54), are improved, the mechanical properties of the paper are improved.
    Example 3. The conditions of example 1 are reproduced, except that after forming a paper sheet, it is impregnated with starch at the rate of 5 g / m2 with an appropriate device,
    The control sample is impregnated with starch, but not treated with enzymes.
    Note the following mechanical properties:
    Test Example 3
    sample Break rate 2,82,65
    CMT161164
    Note the preservation of mechanical properties at a high level. Compared with the control sample of example 1, the treatment carried out under the conditions of example 3, allows not only to lower the SR, but also to improve the mechanical properties.
    Example 4 Reproduce the conditions of example 2, subjecting the paper to starch treatment as described in example 3.
    The control sample is impregnated with starch, but not treated with enzymes and not refined by mechanical means.
    The following mechanical notes are noted:
    Test Example 4
    sample
    Gap rate of 2.82.82
    CMT161174
    An even more distinct improvement in mechanical properties is noted than the improvement noted in Example 3.
    Example 5. The conditions of example 1 are reproduced, but the max 2000 CL 2000 is replaced with a cellulose 250 R, marketed by GENENCOR. This enzymatic composition in liquid form is characterized by the following USI activity / kg of powder:
    Ci (AVI CEL) 0.008
    Cx (SMS) 0.12
    Xylanase 0.11
    FPU0.26
    5 Also, the initial paper pulp, consisting of 75% CCR (recycling cardboard boxes) and 25% non-gauge from the warehouse, is also changed, and a 3% aqueous suspension is made of it, 0 FD is reduced from 39.5 to 29.5,
    The following mechanical properties are noted (measurements made with a laboratory formatting 120 g / m maintained at 23 ° C at 50% relative humidity 5):
    Test Example 5
    sample
    Gap Indicator 1,761.65
    SMT98,792.3
    0I gum 6. Reproduces the conditions
    according to example 5, the replacement of cellulase 250P with the enzymatic composition SR 249, a derivative of the microorganism Aspergilius niger and marketed by the company NEW 5 (NOVO).
    This liquid enzyme composition is characterized by the following activity, USI / m solution:
    Ci (AVICEL) 8
    0 Cx (SMS) 108
    Xylanase 560
    FPU1
    This composition is administered at a concentration of 2.65% by weight of dry weight. 5 SHR reduced from 34.5 to 27.
    Note the following mechanical properties:
    Test Example 6
    sample
    0 break rate 21.95
    CMT127125
    Note the aging of mechanical properties.
    Example 7. Under the same conditions as 5 of Example 1, a 5% aqueous suspension of paper pulp, consisting of 100% of oversize from the warehouse, is obtained. Introduced 0.25 wt.% Dry weight of the enzymatic composition of example 1.
    ShR is reduced from 48 to 35.5.
    Note the proper mechanical properties.
    Example 8. A chemical Kraft mass with short bleached fibers is obtained, from which a 5% suspension is made as in Example 1. Except that the enzymatic composition is introduced at a concentration of 0.25 wt.% Dry weight and the reaction is carried out. enzymes for 60 min.
    Before the enzymatic treatment, the mass is refined mechanically, the argument is SR from 18 to 25. After the enzymatic treatment, it is noted that the SR decreased to 20.
    For chemical masses, indicative mechanical properties are other properties than those for masses consisting of recycled fibers, due to the different qualities imposed on paper.
    The gap rate is also noted, as well as the breaking length under tension.
    The tensile length under tension is determined according to the conditions defined by the standard NFQ 03 004. This calculated length limit, over which a uniform paper strip of some width, supposedly suspended at one of its ends, breaks under the action of its own weight.
    Note the following mechanical properties:
    Test Example 8
    sample
    Gap indicator 1,291.28
    Breaking length, m 25352546
    Compared with the control sample, it is noted that mechanical properties are maintained.
    Example 9. The same conditions as in Example 8 are reproduced, but the mass is preliminarily refined mechanically to obtain SR of about 31. After enzymatic treatment, SR is lowered to 22.
    Note the following mechanical properties:
    Test Example 9
    sample
    Break rate 1,401.45
    Breaking length, m 28002820
    Compared to Example 8, it is noted that when starting from a higher initial SR, the use of which leads to the production of paper with better mechanical properties, it becomes easier to lower the SR without disturbing the mechanical properties. For example, have not only satisfactory mechanical
    properties, but also good paper machine performance. In Example 8, the SR decreased from 25 to 20 after enzymatic treatment, i.e. a decrease of 20%. In Example 9, the RR decreased from 31 to 22 after identical enzymatic treatment, i.e. a decrease of 29%.
    Example 10. Get chemical Kraft mass of bleached long fibers, from which make 5% suspension. The conditions are identical to those of Example 8, except that the pH of the medium is adjusted to 6, and the temperature is brought to 20 C.
    The initial SR is 12, the mass is subjected to mechanical refining before enzymatic treatment, which brings the SR to 25. After enzymatic treatment, it decreases to 21.
    Therefore, it is noted that changes in the temperature and pH conditions do not interfere with the action of the enzymes.
    Note the following mechanical properties:
    Test Example 10
    sample
    The gap rate 4,744,58
    Breaking length, m 51735052
    Compared to untreated enzymes, a mechanically refined control sample, preservation of the level of mechanical properties is noted. The higher breaking lengths of the control sample and example are the result of the mass containing long, not short fibers.
    Example 11 (by a known method). An aqueous suspension of paper pulp based on recycled fibers consisting of 100% regenerated cardboard boxes is prepared in the reactor. Prepare an aqueous suspension of 30 g / l. The suspension is heated to 45 ° C and the pH is 6. FP is 43.
    A retention agent (or flotation agent) based on polyacrylamide is added at a rate of 0.02% by weight relative to the weight of the fibers. After 30 minutes, RR is measured, it is equal to 38.
    Example 12. In an aqueous suspension of Example 11, instead of the flocculation agent, additives of O, 1% by weight of an enzymatic composition based on cellulase and hemicellulase, for example, a commercial solution with the name Multiffect L250TM. manufactured by Finnish Sugar Co. Ltd. After 30 minutes, RR is measured at 28.
    Example 13 To the aqueous suspension of example 11, 0.02 wt.% Of the flocculation agent and 0.1 wt.% Of the enzymatic are added.
    the composition used in Example 12. After 30 minutes, the PN is 25.
    Examples 11-13 show that the addition of the agent flocculim reduces SR, the addition of the enzymatic composition further reduces SR, both additives have a greater effect than one.
    Example 14. A paper for covering cartons of specific gravity of 125 g / m2 was manufactured using an industrial papermaking machine.
    The starting fibrous material consists of 95% by weight of regenerated cardboard boxes and.% Bulk material from the warehouse. Using a pulper, an aqueous suspension of a concentration of 30 g / l is continuously prepared. This suspension is then passed through various cleaners and conventional storage vats. A flocculation agent based on polyacrylamide, namely, the product sold under the name Disidret 313 P, at the rate of 0.02 May,% of the dry mass of the finished paper, is added to the composition. When the suspension reaches a temperature of 45 ° C and a pH value of 6, an enzymatic preparation based on cellulase and hemicellulase at the rate of 1.2 l / t of dry finished paper of the product sold under the name Multifect L 250 TM of Finnish Shugar Co. Ltd. is introduced into it. The reaction is carried out during the passage of the suspension in the tank, which lasts approximately 30 minutes.
    The suspension treated with enzymes is then fed to the head box, where its concentration is adjusted to 7.4 g / l. The degree of PS of the suspension is about 40.
    The composition is poured onto a sheet of paper machine that operates at a speed of 250 m / min.
    Thus, 4.15 t / h of coating paper is obtained.
    The rupture indicator is measured according to the standard NFQ 03 053. This indicator is the quotient of dividing the evenly distributed maximum pressure maintained by the paper sample, perpendicular to the surface, by the paper weight. The break rate is 1.79.
    Example 15 (by a known method). The operation is the same as in Example 1, except that it does not process enzymes, and a flocculation agent based on polyacrylamide, namely, the product sold under the name Desidret 313 P, is added to the paper stock, at a rate of 0.02 wt.% of the dry weight of the finished paper.
    The concentration in the head box is 9.5 g / l, providing the best compromise between proper dehydration and maximum capacity. The degree of FF is about 50. The resulting capacity is 3.89 t / h. The paper break rate is 1.64.
    The use of enzymatic compounds provides greater solubility in the head box and an increase in the speed of the machine, while increasing productivity. Improved paper performance is also observed.
    Example 1b (by a known method). The operation is the same as in Example 15, except that 0.5% by weight of the flocculation agent is added based on the dry weight of the finished paper.
    The concentration in the head box is 9.5 g / l. With such a composition it was impossible to make a sheet of paper. A large number of flocculation agents have a negative effect on leafing.
    The table gives examples 17-33, carried out as example 1, only at different concentrations of enzymes, pH, processing temperature and time.
    As can be seen from the data in the table, at an enzyme concentration of 0.01% (Example 17), a further decrease in HR is observed. On the contrary, no decrease is detected at 0.005%.
    A large amount of enzyme (example
    20), although it allows a significant reduction in HR. causes damage to the mechanical properties of the paper produced. In addition, the cost of the method becomes very high.
    At pH 2 (Example 22), the enzymes are destroyed and their action is zero. At pH 9 (Example 24), enzymes also have no significant effect.
    Temperature too low (example
    26) does not provide a significant effect of enzymes. Too high a temperature (Example 28) destroys the enzymes, and their action is again negligible.
    Too short an operation time (Example 30) is ineffective, even at elevated concentrations (Example 32).
    At too low a concentration, even for a very long time, the effect is insignificant.
    Thus, the proposed method can significantly improve the dewatering of paper pulp with a high degree of SR and increase the productivity of the paper machine.
    权利要求:
    Claims (6)
    [1]
    1. A method for dewatering paper pulp, including treating it with a chemical reagent and pouring a paper web, characterized in that, in order to intensify the process while maintaining the mechanical strength of paper, an enzyme preparation containing cellulases and / or hemicellulases from cultures of Trlchoderma microorganisms is used as a chemical reagent virtdae or Aspergillus niger in an amount of 0.01-2.0% by weight of dry fiber, while the enzyme preparation is introduced into the pulp with a degree of grinding equal to or higher than 25 ° SHR.
    [2]
    2. The method according to claim 1, wherein the treatment with enzyme preparation
    five
    the volume is carried out at 20-60 ° C, preferably 50 ° C, and for 30-60 minutes.
    [3]
    3. Method according to paragraphs. 1-2, characterized in that use paper pulp With a pH of 3-7.
    [4]
    4. Method according to paragraphs. 1-3, characterized in that they use an enzyme preparation with a Ci activity (AVICEL) of 0.168 sr. units / mg of powder, Cx activity (CMC), equal to 3.91 conventional units / mg of powder, and xyl-acid activity of 31 services. unit / mg powder.
    [5]
    5. Method according to paragraphs. 1-4, characterized in that the pulp is made from recirculated fibers.
    [6]
    6. Method according to paragraphs. 1-5, characterized in that the pulp is refined mechanically before the treatment with the enzyme preparation.
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    同族专利:
    公开号 | 公开日
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    CA1340724C|1999-09-07|
    US4923565A|1990-05-08|
    NO172858B|1993-06-07|
    JPH07107234B2|1995-11-15|
    NO172858C|1993-09-15|
    DE3782602D1|1992-12-17|
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    申请号 | 申请日 | 专利标题
    FR8613208A|FR2604198B1|1986-09-22|1986-09-22|PROCESS FOR TREATING A PAPER PULP WITH AN ENZYMATIC SOLUTION.|
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