Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
  • D21B1/00—Fibrous raw materials or their mechanical treatment
  • D21B1/02—Pretreatment of the raw materials by chemical or physical means
  • D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
  • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
  • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
  • B27N3/08—Moulding or pressing
  • B27N3/10—Moulding of mats

Definitions

• 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.
• 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.
• 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.
• 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.
• pectinase has been specifically used in post-treatment of mechanical pulps.
• 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.
• 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.
• 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.
• a chelating agent for instance DTPA and/or sulfite
• 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 can be de-esterified through for instance alkaline treatment and thus contributing to swelling.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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:
• suitable mechanical means for instance compression with screw device or roll press device
• 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.
• 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.
• 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.
• 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.
• pectinase enzyme 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the embodiment as described here can be modified according to the source of fiber material and the process set-up.
• 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.
• 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.
• 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
• 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.
• 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.
• 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.
• the obtained pulps are evaluated both for strength properties and optical properties including a bleachability study with hydrogen peroxide bleaching.
• Sample 1 TMP condition with only water impregnation with pH adjusted to 5.
• Sample 2 TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
• Sample 3 HI-TMP condition with only water in the impregnation adjusted to pH 5.
• Sample 4 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
• the enzymatic treatment has a surprising effect on energy reduction also with the high intensity condition.
• 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.
• Sample 3 HI-TMP condition with only water in the impregnation adjusted to pH 5.
• Sample 4 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH
• Sample 5 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4 kg/t DTPA, pH 5.
• 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.
• 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.
• Pulps with different treatments are bleached with alkaline peroxide with following bleach conditions:
• Sample 7 TMP condition with only water impregnation with pH adjusted to 5.
• Sample 8 TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
• Sample 9 HI-TMP condition with only water in the impregnation adjusted to pH 5.
• Sample 10 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH
• Sample 11 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4 kg/t DTPA, pH 5.
• 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.
• 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.

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