CN103109015A - Freeness of paper products - Google Patents

Freeness of paper products Download PDF

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Publication number
CN103109015A
CN103109015A CN2011800371167A CN201180037116A CN103109015A CN 103109015 A CN103109015 A CN 103109015A CN 2011800371167 A CN2011800371167 A CN 2011800371167A CN 201180037116 A CN201180037116 A CN 201180037116A CN 103109015 A CN103109015 A CN 103109015A
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Prior art keywords
paper
paper pulp
pulp
hydrogen peroxide
catalyst
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CN2011800371167A
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CN103109015B (en
Inventor
R·哈格
K·S·杨
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Borchers Catalyst UK Ltd
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Catexel Ltd
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    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/20—Methods of refining
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1078—Bleaching ; Apparatus therefor with Mn-containing compounds
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00—Wet end of machines for making continuous webs of paper
    • D21F1/0009—Regulating the freeness of the pulp

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Catalysts (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The present invention provides for the optimisation of conditions for treating pulp with a catalyst and hydrogen peroxide to produce a Freeness value (SR) in a web produced from the treated pulp such that the energy required in mechanical agitation of the pulp is reduced.

Description

The freedom of paper product
Invention field
The present invention relates to new paper pulp process for purification.
Background of invention
The paper pulp (pulp) of making paper, paper handkerchief (tissue), cardboard (board) or Related product can be obtained by the cellulose from timber and other source (for example hemp, straw, cotton).Most raw materials are wood pulp, and it can be cork raw material or hardwood raw material.Cork fibrous carries the coniferous tree of pin such as pine tree, dragon spruce, alpine fir, pesudotsuga taxifolia.Hardwood fiber from various types of deciduous trees such as birch, eucalyptus and acacia.Mechanical pulp contains most of initial wood mass element, and most of lignin is removed in chemical pulp.
Difference difference between cork (SW) and hardwood (HW) is the length of the individual fibers cellulose fiber of timber, the roughening of fiber and the rigidity/conquassation of fiber.
Hardwood and cork must stand concrete mechanical treatment (making with extra care) so that wood conversion is the fibre pulp that is used to form paper net width.The fiber of cellulose paper mass suspension is through the character of mechanical treatment with the change fiber.The cellulose paper mass suspension is processed into product, described product is compared with initial cellulose paper mass suspension, has freedom (Shopper-Riegler) value of the stretching of increase/tearing strength character, increase, the fineness that increases and improved paper/paper handkerchief and makes character.The freedom value that increases causes the water separation capability that paper/paper handkerchief is made that reduces, and this has increased required energy and the paper production speeds that can slow down of dry paper.On the other hand, too low freedom produces firm not paper/paper handkerchief.Refining have importance to the two character of chemical pulp and mechanical pulp.Except dehydration, should also be noted that energy consumes high during subtractive process.
Open in WO 2005/028744 by the chemical method of regulating cellulose fibre with molysite and hydrogen peroxide treatment fiber; The fibre property that the processing generation of Kraft softwood pulp and hardwood fiber are similar.
What WO 2004/022842 disclosed after processing with pectase refiner mechanical pulp reduces energy approach, the paper pulp that has specific freedom character with production.
EP 0458397 discloses use manganese Isosorbide-5-Nitrae, 7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane (Me 3-TACN) complex compound is as bleaching and oxidation catalyst, and the purposes that is used for textiles and dioxde pulp bleaching process.
U. S. application 2001/0025695A1, Patt etc. disclose use 1,2-two-(4,7-dimethyl-Isosorbide-5-Nitrae, three azacyclo-ninth of the ten Heavenly Stems of 7--1-yl)-ethane (Me 4-DTNE) and Me 3The ClO of the manganese complex of-TACN 4 -And PF 6 -Salt is used for respectively wood pulp delignification and bleaching.Simultaneously comprise Me in use 4During the manganese compound of-DTNE, report do not have viscosity loss or viscosity loss little; Comprise Me in use 3During the manganese compound of-TACN, viscosity loss is much bigger.Known have more low viscous cellulose and obtain the paper that intensity reduces (C.W.Dence, D.W.Reeve edits, Tappi, Atlanta, 1996 for Pulp Bleaching, Principle and Practice (association with pulp bleaching principle and put into practice)).
WO 2007/125517 disclose use 1,2-two-(4,7-dimethyl-Isosorbide-5-Nitrae, three azacyclo-ninth of the ten Heavenly Stems of 7--1-yl)-ethane (Me 4-DTNE) and Me 3-TACN and buffer and chelating agent are used for bleached cellulose matrix.
WO 2008/086937 disclose use 1,2-two-(4,7-dimethyl-Isosorbide-5-Nitrae, three azacyclo-ninth of the ten Heavenly Stems of 7--1-yl)-ethane (Me 4-DTNE) and Me 3-TACN is used for bleached cellulose matrix, keeps simultaneously pH constant.
US 2002/0066542 A1 has described transition metal (particularly cobalt) complex compound of multidentate ligand, and the purposes of this compounds in delignification and method for bleaching.With comprising Me 3The reference experiment that the manganese complex of-TACN carries out shows significant viscosity loss, and other compound of describing does not show that significant viscosity changes.
The method that expectation provides the permission paper/paper handkerchief producer to use the subtractive process with reduced levels freedom, described method produce and by the common identical pulp strength character that provides of mechanical means.
Summary of the invention
We find, have improved the effect made from extra care these fibers with transition metal complex and the hydrogen peroxide treatment cellulose fibre of preformed azepine ring molecule.Processing can before subtractive process, during or afterwards, usually before subtractive process or during carry out.Improved refining character can be observed by the tensile strength properties that can input in same mechanical and identical Shopper-Riegler value (SR) increases down.
In addition, although admit extensively that in paper pulp/paper field the obvious minimizing of cellulose viscosity loss do not expect for Papermaking Properties, and comprise Me 3The use of the Mn catalyst of-TACN produces significant viscosity loss, according to different research, and unexpected especially discovery, the use of this class catalyst causes subtractive process for the improvement of the effect of fibre property.
The present invention can be applicable to chemical pulp and mechanical pulp, comprises recycled pulps, for the production of paper, paper handkerchief or cardboard.
We find that the energy consumption and the time that form the cellulose paper mass suspension can reduce under the effect of Mn catalyst together with hydrogen peroxide, described cellulose paper mass suspension can further be processed into has the paper that improves freedom.
first aspect, the invention provides the method for processing the cellulose paper mass suspension, it comprises (i) makes cellulosic pulp fibers stand the step of the aqueous solution of manganese transition-metal catalyst that pH is 6-13 and hydrogen peroxide, (ii) make paper pulp stand subtractive process until Shopper Riegler (SR) value reaches 10-90 °, and the paper pulp that generates is processed into paper, paper handkerchief or cardboard, wherein the concentration of manganese transition-metal catalyst existence is 0.0001-1kg/ ton oven dry paper pulp, and the concentration that hydrogen peroxide exists is 0.1-100kg/ ton oven dry paper pulp, the manganese transition-metal catalyst is pre-formed monokaryon Mn (II), Mn (III), Mn (IV) or double-core Mn (II) Mn (II), Mn (II) Mn (III), Mn (III) Mn (III), Mn (III) Mn (IV) or Mn (IV) Mn (IV) transition-metal catalyst, the part of transition-metal catalyst is formula (I):
Figure BPA00001673723200031
Wherein:
Figure BPA00001673723200032
P is 3;
R independently is selected from: in hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl or R one is connected to by ethylene bridge on the N of another Q of another ring.
R 1, R 2, R 3And R 4Independently be selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
second aspect, the invention provides pH and be the aqueous solution of the manganese transition-metal catalyst of 6-13 and hydrogen peroxide for increasing the purposes of the increase degree of freedom value in subtractive process of cellulosic pulp fibers, wherein the manganese transition-metal catalyst is pre-formed monokaryon Mn (II), Mn (III), Mn (IV) or double-core Mn (II) Mn (II), Mn (II) Mn (III), Mn (III) Mn (III), Mn (III) Mn (IV) or Mn (IV) Mn (IV) transition-metal catalyst, the part of transition-metal catalyst is formula (I):
Figure BPA00001673723200041
Wherein:
Figure BPA00001673723200042
P is 3;
R independently is selected from: in hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl or R one is connected to by ethylene bridge on the N of another Q of another ring.
R 1, R 2, R 3And R 4Independently be selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
According to the specific embodiments of the first and second aspects of the present invention, each R in formula (I) part independently is selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl.For these not the part of bridge joint be especially unexpectedly, wherein, not having R to be connected to by ethylene bridge on the N of another Q of another ring is suitable for using according to the inventive method, because prior art proves, when carrying out the delignification reaction with the transition-metal catalyst that comprises this class part, find that viscosity reduces.
On the other hand, the invention provides can be by according to the method for first aspect present invention or the paper, paper handkerchief or the cardboard that obtain according to the purposes of second aspect present invention.
Freedom value (SR) is the canonical measure value of measuring by Shopper Riegler method as Drainability NORM EN ISO 5267-1; The freedom value (SR) that is used for this paper is measured by this method.
The concentration of catalyst and hydrogen peroxide will be influential to the required time of paper pulp refinement treatment, as the ratio of the amount of the activating agent of pulp quality and use.In this, be optimal conditions, the variable of surfactant concentration, temperature, pH and time is changeable variable.
Be preferably 1 minute-4 hours with catalyst and hydrogen peroxide to processing time of paper pulp, more preferably 5 minutes-3 hours, and most preferably 10 minutes-2 hours.Further, preferably use the temperature of the process of catalyst and hydrogen peroxide to be 30-95 ℃, more preferably 40-90 ℃.Use the pH of the process of catalyst and hydrogen peroxide to be preferably pH 8-12.
Transition metal complex and hydrogen peroxide can add in the conventional bleaching stage.Perhaps, transition metal complex and hydrogen peroxide can before refining stage or during add, for example add in the paper pulp (being chemical pulp) of having bleached in one or more delignifications and bleaching stage.The chemical pulp of processing like this can be by contacting and delignification/bleaching (for example defining according to the present invention) with transition-metal catalyst with hydrogen peroxide.Perhaps, chemical pulp can be bleached (for example using ozone, chlorine dioxide) by the non-catalytic of for example paper pulp in addition or produce with the bleaching of hydrogen peroxide non-catalytic.
Perhaps, Mn catalyst all can be at bleaching stage together with hydrogen peroxide, also have after bleaching stage, before refining stage or during use.
For mechanical pulp and recycled pulps processing, often carry out bleaching stage (for example relating to the use of hydrogen peroxide).The manganese transition-metal catalyst that also can comprise in the case, the first and second aspect definition according to the present invention.Sometimes, can process recycled pulps (not adding the manganese transition-metal catalyst for this blanching step) with the reducibility blanching step of dithionite.Perhaps, manganese transition-metal catalyst and hydrogen peroxide can be used for processing machine paper pulp and recycled pulps, especially before the machine finish process or during, at it with hydrogen peroxide and/or with after dithionite bleachings.
Perhaps, Mn catalyst all can be at bleaching stage together with hydrogen peroxide, and again after bleaching stage, before refining stage or during use.
These possibilities discuss in more detail following.Between the interpolation and subtractive process of transition-metal catalyst and hydrogen peroxide (if the former carried out before the latter), usually but must not carry out washing step.
The amount that should understand the transition-metal catalyst/hydrogen peroxide of paper pulp per ton (oven dry) needs is mainly mol ratio, but commonly uses the weight amount of expression in industry.In this, the scope of the transition-metal catalyst that paper pulp per ton (oven dry) needs is the scope of 0.0001-1kg/ ton paper pulp (oven dry), this equates about 0.1-1500mmol/ ton paper pulp (oven dry).According to specific embodiments of the present invention, the scope that has concentration of transition metal is 0.0005-0.2kg/ ton paper pulp (oven dry).The scope of the hydrogen peroxide (100%) of paper pulp per ton (oven dry) is 0.1-100kg, more preferably 0.5-50kg, most preferably 1-30kg.For example, the scope of the hydrogen peroxide (100%) of paper pulp per ton (oven dry) can be 0.1-25kg/ ton paper pulp (oven dry).The concentration range that should understand each transition-metal catalyst disclosed herein can combine with the scope of each hydrogen peroxide disclosed herein.For example, according to certain embodiments of the present invention, the scope that has concentration of transition-metal catalyst is 0.0005-0.2kg/ ton paper pulp (oven dry), and hydrogen peroxide (100%) scope of paper pulp per ton (oven dry) is 0.1-25kg.
Transition-metal catalyst: the preferable range of the mol ratio of hydrogen peroxide is 1: 100-1: 10000.
Remembeing above content, is conventional for those skilled in the art below: determine that by repetition test condition is to produce freedom value (SR) and to use this condition to obtain and to optimize at the industrial paper pulp that the net width is had the freedom value (SR) of expectation.
Detailed Description Of The Invention
The paper pulp of producing the Paper or cardboard grade is fed in paper machine, and it forms paper net width and therefrom dewaters by pressurization and drying in paper machine.Pressurization is removed water by power to paper.In case water leaves from paper is stressed, collects water with felt.When with hand-made papermaking, use the oil suction paper.Paper pulp for the manufacture of paper handkerchief or kitchen toilet paper grade dewaters without pressurization and drying, to keep suitable absorbance and smoothness character.
Drying relate to use air and or heat with from paper except anhydrating.At the initial stage of papermaking, this realizes by paper is hung up as the laundromat.In more modern, use various forms of heat drying apparatus.On paper machine, modal is steam-heated drying chamber.These drying machines can be heated to above the temperature of 200 ℉ (93 ℃) and use in the long sequence more than 40 tanks.Heat with these generations can be dried to paper less than 6% moisture easily.
Exist concrete program to produce tissue.With reference to Paper and Board Grades (paper and board grades), Book 18, the 4 chapters, Finnish Paper Engineers ' Association and TAPPI (2000).
We find to change paper pulp to the extent of reaction (measuring by its freedom value (Shopper-Riegler-SR)) of machine finish process, to produce the net width of being made by the cellulose paper mass suspension with manganese transition-metal catalyst and hydrogen peroxide treatment cellulose paper mass suspension.But before processing machine finish by Mn catalyst, during or carry out after the machine finish process.For example, and as discussed below, catalyst/hydrogen peroxide can add to after machine finish in paper pulp blend or paper pulp storage pool, and wherein paper pulp can be stored before dehydration.
Ratio between TENSILE STRENGTH and freedom is improved, that is, under identical freedom value strength increase or under low freedom value intensity identical.Obtain the best freedom value of final products by the monitoring treatment conditions.Further, at the identical refining lower volume that can reach increase, to the tissue particular importance.
We find to process cellulose paper mass suspension and monitoring concentration and the best freedom value of the variable of time different periods of permission.
Term oven dry paper pulp be paper pulp 100-105 ℃ of drying to obtain the paper pulp of constant weight.With reference to TAPPI-test T240om-93 (1993).
Refining
Different types of equipment is usually used in the mechanical treatment cellulose pulp.Agitator (comprising the Hollander agitator) uses in many factories, but is now replaced by conical refiner and disk refiner (can move in continuous process) in a large number.Conical refiner comprises shallow angle refiner (Jordan), middle angle refiner (Conflo) and wide-angle refiner (Claflin).The refining unit of disk comprises three types: table roller, two disk, many disks refiner.
Refining can carrying out under low denseness (2-6%), medium consistency (10-20%) or high-consistency (30-35%).The demand that depends on final products can be made different selections for the denseness processing of the best.With reference to Paper and Board Grades (paper and board grades), Papermaking Part 1.Stock Preparation and Wet End (papermaking part 1. raw material preparation and green ends), Book 18, the 4th chapter, Finnish Paper Engineers ' Association and TAPPI (2000).
Processing can be mode in batches or continuously, because cost reason and quality control are easier to, and the preferred latter often.
Under many circumstances, with different types of wood pulp such as softwood pulp and bardwood pulp are mixed.One of them or both can independently make with extra care.Uses of often connecting of more refiner, with enhancing benefit/energy requirement with pulp treatment.
Refining can carrying out chemical pulp, mechanical pulp and recycled pulps, these are all objects of the present invention.
Depend on application, can carry out the refining of varying level.For paper handkerchief and kitchen toilet paper grade, hang down and make with extra care, to guarantee good volume, pliability, absorbance and brightness.Low refining be of value to above character, but negative effect intensity property.Therefore, often add wet strength agent and/or dry strength agent.After refining, often obtain the Shopper-Riegler value of 10-30 °.
For printing paper and writing paper, impressionability and mechanical performability are key parameters.Paper must be clean and bright, has suitable slickness, compressibility, soaks black ability and enough intensity is used for printing operation.Minimum opacity is another key character.Therefore, these paper need good refining control to be used for its final use to produce the correct smoothness of internal bond strength and acquisition and moulding level.Bleached paperboard grade (be used for packing frozen food and liquid, and be used for cardboard and dixie cup) needs good rigidity and volume and suitable slickness and impressionability.Inner combination, wrinkle resistance and DIMENSIONAL STABILITY are also key factors.Therefore also need refining to obtain these character (reducing volume and rigidity and exceed) fully.These application often need the Shopper-Riegler value after 15-50 ° making with extra care.
Fine and close paper needs the refining of significant quantity, depends on the specific products needs.Release-Ji paper, glassine paper and greaseproof paper all need to make with extra care widely the intensity that obtains expecting and the balance of appearance characteristics.If especially purpose is to make cellophane paper, subtractive process needs a large amount of energy requirements.SR value that can be up to 90 °.
Mechanical pulp often needs the refining Paper or cardboard material that presents suitable physical character with production.When refiner mechanical pulp, often reach the Shopper-Riegler value of 20-80 °.
But refining degree on-line monitoring.The energy input is to determine the refining most important parameter of degree.Exist control system with on-line monitoring subtractive process and adjusting energy input as requested.Probe monitoring refiner load, variations in temperature, mobile/denseness, draining/freedom (SR) etc.Main state-variable comprises temperature, pH, denseness, additive, preliminary treatment, productivity ratio and applies energy.
By Mn catalyst and hydrogen peroxide treatment cellulose fibre
Using Mn catalyst and hydrogen peroxide treatment cellulose fibre can the different phase during fiber treatment/paper-making process carry out.This can be before the machine finish process, during the machine finish process or after the machine finish process, usually before the machine finish process or during.
Usually paper pulp, the chemical pulp of having bleached in one or more delignifications and bleaching stage can be used for further processing to produce paper handkerchief, Paper or cardboard.Yet, within the scope of the present invention, also can use the paper pulp (mechanical pulp) or the recirculation wood pulp that contain lignin.For integrated factory, bring the wet pulp slurries into paper mill.When the paper producer obtains paper pulp from other factory, first pulpboard is put into the pond and decomposed to obtain the pulp slurry that further to process of dilution.
In the pulp mill, chemical pulp is generally by hydrogen peroxide and/or use ozone for example or other bleaching bleaching of chlorine dioxide.Mechanical pulp and recycled pulps often use hydrogen peroxide bleaching to increase brightness of pulp.During one or more these bleaching stages, can use hydrogen peroxide together with the cellulose of Mn catalyst to obtain to process in subtractive process.Mn catalyst and hydrogen peroxide can add during the different phase of pulp mill.
In the paper pulp blender, chemicals is added in paper pulp, subsequently it is mixed very up hill and dale.Within the scope of the present invention, catalyst and hydrogen peroxide can be added in the paper pulp blender to complete pulp processing.This can carry out in low denseness blender (continuous mixer, tower blender, dynamic mixer or static mixer), medium consistency blender (bolt blender, high-shear mixer) or high-consistency blender (comprising Kneader and collar plate shape blender).In the boiling blender, steam is added in paper pulp to increase the paper pulp temperature.Also catalyst and hydrogen peroxide can be added in the paper pulp of boiling blender.
With reference to Pulp Bleaching, Principleand Practice (association with pulp bleaching principle and put into practice), C.W.Dence, D.W.Reeve edits, Tappi, Atlanta, 1996, infra).
Add the association with pulp bleaching chemicals in blender after, most of association with pulp bleaching carries out in bleaching tower, thereafter washing pulp.Because bleaching process is slow (normally 2-4 hour) generally, bleaching tower trends towards greatly.Yet, sometimes also use less paper pulp to be detained pipe to allow some bleaching or processing reaction to occur.Because process is generally continuous, paper pulp is (upflow tower) upwards, downwards (downflow tower) or slowly move under its combination (upper reaches-downflow tower).Within the scope of the present invention, but by catalyst and hydrogen peroxide treatment much shorter, allow relatively little treating column.
In washer, the paper pulp with chemical treatments is rinsed in the previous stage of processing procedure usually.For example, acid chlorine dioxide NaOH solution washing is with except the soluble lignin residue of lixiviating and be fabricated to the paper pulp of next stage preparation.Within the scope of the present invention, Mn catalyst and hydrogen peroxide can be added in (other) blender, utilize its fast reaction kinetics catalyst treatment paper pulp.
The design of paper pulp storage tower is used for storing paper pulp with further processing over time.Usually this class storage tower can be before the process of carrying out the association with pulp bleaching stage, or after final bleaching stage, finds before for example being transported to the paper mill.Catalyst and hydrogen peroxide can add together with the paper pulp that enters this storage tower, allow the slow processing procedure of paper pulp.
Pulper is used for dilution waste paper (de inked pulp) and adds alkali and hydrogen peroxide is used for the bleaching of de inked pulp.Mn catalyst can be added in this pulper, to allow by the catalyst treatment de inked pulp.
Mn catalyst and hydrogen peroxide also can add cellulose pulp to before the subtractive process in paper mill in, such as in pulper, high-density paper stock tank, paper pulp eliminating potential pool, paper pulp mixing pit or paper pulp homogenize pond.Pulper and high density pond are usually used in then mixing with water and but dried feed, semi-finished product and recyclable papers being prepared into the pumping state by adding water.In the paper pulp mixing pit, make two or more dissimilar paper pulp (optional through refining) mix and store with further processing, such as softwood pulp and bardwood pulp.The denseness of wood pulp is reduced to aspiration level in the homogenize pond.
Mechanical pulp is everlasting and is processed to process the fiber of distortion (kink, curling or spiral) in eliminating potential pool.Usually mechanical pulp is diluted to the denseness of 1-2%, is heated to 70-90 ℃, stirs at least 20 minutes, after this with its further processing.Be similar to above-mentioned paper pulp and store, the paper pulp storage pool is used for storing wood pulp.Other above-mentioned pond is also processed in following process through the steady flow that is usually used in storing wood pulp and guaranteeing paper pulp.Wood pulp can be delivered from association with pulp bleaching factory, perhaps its (integrated factory) production on the spot.
Perhaps catalyst/hydrogen peroxide can add before the paper pulp refiner and allow during subtractive process and fibrin reaction.Due to heat release during making with extra care, for the other energy requirement that obtains the optimization process effect by catalyst will reduce or not exist.Can use different purification apparatus, it comprises agitator; The Hollander agitator; Shallow pyramid refiner; Middle pyramid refiner; The wide-angle conical refiner; The table roller refiner; Two disk refiners; Many disks refiner.With reference to Paper and Board Grades (paper and board grades), Papermaking Part 1.Stock Preparation and Wet End (papermaking part 1. raw material preparation and green ends), Book 18, the 4th chapter, Finnish Paper Engineers ' Association and TAPPI (2000) and C.F.Baker, Tappi Journal, 78,147,1995.
At last, catalyst/hydrogen peroxide can add after the stage at machine finish, for example in paper pulp blend pond (wherein with different wood pulp source mixing) or paper pulp storage pool.For example mechanical pulp can be processed like this.
Perhaps, Mn catalyst all can be at bleaching stage together with hydrogen peroxide, and again after bleaching stage, before refining stage or during use.
Transition-metal catalyst
The manganese transition-metal catalyst that uses can be by using counter ion such as PF 6 -Or ClO 4 -And be nondeliquescent.Yet for industrial substrate, preferred transition metal complex is water miscible.The form that preferred preformed transition metal is salt makes its water-soluble 30g/l of being at least, for example 50g/l at least under 20 ℃.Preferred salt is those in chloride, acetate, sulfate and nitrate.These salt are described in WO 2006/125517.
According to specific embodiments of the present invention, each R in formula (I) part independently is selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl.According to specific embodiment, R independently is selected from: hydrogen, CH3, C2H5, CH2CH2OH and CH2COOH.
Preferably, R 1, R 2, R 3And R 4Independently be selected from: H and Me.
According to specific embodiment, R, R 1, R 2, R 3And R 4Independently be selected from: H and Me.Most preferably, catalyst derives from Isosorbide-5-Nitrae, 7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane (Me 3-TACN).
Preformed transition-metal catalyst salt is preferably has at least one O 2-The double-core Mn (III) of bridge or Mn (IV) complex compound.According to certain embodiments of the present invention, transition-metal catalyst can be complex compound [Mn (IV) 2(μ-O) 3(Me 3TACN) 2] 2+Salt, such as above-described salt.
The application level of Mn catalyst can change with application, but is generally 0.0005-0.2kg/t oven dry paper pulp (o.d.p.).
Hydrogen peroxide
Hydrogen peroxide is as the aqueous solution itself, or as peroxy salt, such as percarbonate etc. provides.Yet, for the cost reason, preferred liquid hydroperoxide.The level that preferably applies hydrogen peroxide is: 0.1kg/t-100kg/t is dried paper pulp (o.d.p.), more preferably 0.3-50kg/t o.d.p. and most preferably 0.5-25kg/t o.d.p.
Reagent preferably provides (pH is as 8-13 the best) take alkaline medium, and its alkalescence preferably provides by NaOH or sodium carbonate.
The temperature of processing procedure is preferably 30 ℃-95 ℃, more preferably 40 ℃-90 ℃.
Using the processing time of catalyst and hydrogen peroxide is 1 minute-4 hours, more preferably 5 minutes-3 hours, and most preferably 10 minutes-2 hours.
Chelating agent
Many chelating agents are suitable for the present invention to be used.Example comprises aminophosphonic acid and carboxylic acid chelating agent, for example aminophosphonic acid and amino carboxylic acid chelating agent.Suitable chelating agent comprises that ethylenediamine tetra-acetic acid (EDTA), polyphosphonate are such as Dequest TMWith non-phosphoric acid stabilize agent such as EDDS (EDDS).
At the preferred amino carboxylic acid chelating agent of the chelating agent that uses together with Mn catalyst and hydrogen peroxide in treatment step or its mixture.Be below the example of preferred amino carboxylic acid chelating agent: ethylenediamine tetra-acetic acid (EDTA), N-hydroxyethylenediamine tetracetic acid (HEDTA), iminodisuccinic acid (IDS), nitrilotriacetic acid(NTA) (NTA), the amino oxalic acid of N-hydroxyethyl, diethylene-triamine pentaacetic acid (DTPA), MDGA (MGDA), EDDS (EDDS) and alanine-N, N-oxalic acid.Most preferred amino carboxylic acid chelating agent is diethylene-triamine pentaacetic acid (DTPA).
Also can use the phosphonic acids chelating agent; Preferred phosphonic acids chelating agent is Dequest 2066 (diethylenetriamines five (methylene phosphonic acid sodium salt).
Should be understood that when using, chelating agent can free acid or the form of salt exist.For example, when existing with the form of salt, it can be the ammonium salt of alkali metal, alkaline-earth metal, ammonium or replacement.Usually, chelating agent (if existence) is in the form of its free acid or is sodium salt, sylvite or magnesium salts.A five sodium-salt that example is diethylene triamine penta(methylene phosphonic acid) of the sodium salt of amino carboxylic acid chelating agent can have been bought by the trade mark of Dequest 2066A on market.
In the solution that contains Mn catalyst and hydrogen peroxide, the most preferred concentration of the chelating agent that uses in described method is 0.01-50kg/ ton oven dry paper pulp, most preferably 0.03-20kg/ ton oven dry paper pulp.
Experiment
Experiment 1: with containing or do not contain [Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2Hydrogen peroxide process softwood pulp (Me at pH 11.0 3-TACN=1,4,7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane).
As open in other places (WO2006/125517), obtained [Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2(be 3.5% the aqueous solution).
Be that 49.9 softwood pulp is handled as follows to initial ISO-brightness: polyethylene (PE) bottle to the oven dry paper pulp of 10% denseness that contains 250g adds 10kg/odtp H 2O 2(odtp=oven dry ton paper pulp-equal 29.4mM H 2O 2) and 7.2kg/odtp NaOH (equaling 18mM NaOH).Depend on experiment, add 0.04kg/odtp[Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2(equal 6.5 μ M[Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2) and 1.0kg/odtp DTPA (diethylene-triamine pentaacetic acid, five sodium-salt)-(ex Akzo Nobel; Trade mark Dissolvine D50; Purity is 50%).Initial pH value is pH 11.0 (measuring under 20 ℃).
Annotate 1: this softwood pulp is at O 2Delignification in-delignification step, and part is further passed through ClO 2The step bleaching.
Annotate 2: in fact, the paper pulp of use contains 35.6% dry and 64.4% water (35.6% dried content).So 702.3g ' is wet ' paper pulp is used for each experiment.
Annotate 3: all experiments are carried out under 10% denseness.
The PE bottle is put into the water-bath (62.5 ℃) 1 hour of preheating and vibrated at bleaching process.Subsequently pulp mixture is filtered and uses a large amount of demineralised water washings by Buchner funnel.Use filtrate, measure H 2O 2Consumption.Below analyze bleached pulp is carried out: kappa value, brightness and intrinsic viscosity.
Experimental result provides in table 1.
Table 1 is used under 60 ℃ at initial pH 11.0
[Mn 2(μ-O) 3(Me 3TACN) 2](CH 3COO) 2、
[Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2With DTPA and need not
[Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2Process the softwood pulp result of 60 minutes.
Figure BPA00001673723200141
The result that gathers in table 1 shows [Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2Interpolation some effects are played in the bleaching of softwood pulp and kappa value, and the viscosity (degree of cellulose polymerization) of softwood pulp is had clearly effect.
The paper pulp of processing is decomposed (DIN EN ISO 5263-1; 2004-12), impact (PFI-grinding machine) (
Figure BPA00001673723200142
EN ISO 5264-2; 2003-05) and the experimental water-based (the Schopper-Riegler method,
Figure BPA00001673723200143
EN ISO 5267-1; 2000-10).
Pass through Rapid- Method preparation experiment chamber handmade paper (
Figure BPA00001673723200145
EN ISO5269-2; 2005-04) and carry out adjusting (the DIN EN 20187 of sample NC 23/50; 1993-11).Below test uses handmade paper to carry out: grams (DIN EN ISO 536; 1996-08), thickness, volume and density (DIN EN ISO 534; 2005-05), air permeability (Bendtsen, ISO 5636/3; 1992-09), tension force, fracture stretching, TENSILE STRENGTH, tensile figure, TEA and elastic modelling quantity (DIN EN ISO 1924-2; 2009-05), internal bond strength (Z direction, TAPPI 541 om-05; 2005), breaking strength, tear index (
Figure BPA00001673723200151
EN 21974; 1994-09).
Result provides in following table.
Impacting and the drainage result of bleached softwood paper pulp after the condition that table 2 provides according to table 1 is processed.
P1: catalyst-free, without DTPA.
P2:[Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2And DTPA
P3:[Mn 2(μ-O) 3(Me 3TACN) 2] (CH 3COO) 2, without DTPA
Figure BPA00001673723200152
Result that table 2 gathers shows, presents similar SR value until 7000 turning in contrast with the pulp sample of catalyst and hydrogen peroxide treatment, turns lower when refining 9000, the SR value of acquisition increase when paper pulp simultaneously.
Table 3 uses as shown in table 2 in 5000 intensity and values of tearing that turn the handmade paper of lower refining paper pulp preparation.
Figure BPA00001673723200153
The result that table 3 gathers shows, with catalyst and hydrogen peroxide treatment then 5000 turn under in the PFI grinding machine refining pulp sample show that the TENSILE STRENGTH, the tensile energy that increase absorb (TEA) and tensile index values, the breaking strength that reduces and tear index, but other parameter is not used the processing of catalyst and hydrogen peroxide significantly to affect (all with respect to the contrast of catalyst-free-P1).When catalyst was combined with DTPA, these tensile strength properties slightly strengthened.

Claims (20)

1. method of processing the cellulose paper mass suspension, it comprises: (i) make cellulosic pulp fibers stand manganese transition-metal catalyst that pH is 6-13 and hydrogen peroxide the aqueous solution step and (ii) make paper pulp stand subtractive process until Shopper Riegler (SR) value reaches 10-90 °, and the paper pulp that generates is processed into paper, paper handkerchief or cardboard, wherein the concentration of manganese transition-metal catalyst existence is 0.0001-1kg/ ton oven dry paper pulp, and the concentration that hydrogen peroxide exists is 0.1-100kg/ ton oven dry paper pulp, the manganese transition-metal catalyst is pre-formed monokaryon Mn (II), Mn (III), Mn (IV) or double-core Mn (II) Mn (II), Mn (II) Mn (III), Mn (III) Mn (III), Mn (III) Mn (IV) or Mn (IV) Mn (IV) transition-metal catalyst, the part of transition-metal catalyst is formula (I):
Figure FPA00001673723100011
Wherein:
Figure FPA00001673723100012
P is 3;
R independently is selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl;
R 1, R 2, R 3And R 4Independently be selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
2. according to claim 1 method, wherein the concentration that exists of manganese transition-metal catalyst is 0.0005-0.2kg/ ton oven dry paper pulp, and the concentration that hydrogen peroxide exists is 0.1-25kg/ ton oven dry paper pulp.
3. according to claim 1 or the method for claim 2, wherein R independently is selected from: hydrogen, CH3, C2H5, CH2CH2OH and CH2COOH.
According to claim 1 to 3 any one method, wherein R, R 1, R 2, R 3And R 4Independently be selected from: H and Me.
5. according to claim 1 or the method for claim 2, wherein catalyst derives from Isosorbide-5-Nitrae, 7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane (Me 3-TACN).
6. according to the method for the claims any one, wherein make paper pulp stand subtractive process until Shopper Riegler (SR) value reaches 10-30 °, to produce tissue.
According to claim 1 to 5 any one method, wherein make paper pulp stand subtractive process until Shopper Riegler (SR) value reaches 15-50 °, to produce printing paper and writing paper.
According to claim 1 to 5 any one method, wherein make paper pulp stand subtractive process until Shopper Riegler (SR) value reaches 50-90 °, with production tracing paper and cellophane paper.
According to claim 1 to 5 any one method, wherein make mechanical pulp stand subtractive process until Shopper Riegler (SR) value reaches 20-80 °.
10. according to the method for the claims any one, wherein catalyst and hydrogen peroxide are added in the paper pulp in equipment, described equipment is selected from: pulper; The high-density paper stock tank; Washer; The paper pulp eliminating potential pool; Paper pulp homogenize pond; The paper pulp mixing pit; The paper pulp refiner; Paper pulp thinning tank and paper pulp storage pool.
11. method according to claim 10, wherein the paper pulp refiner is selected from: agitator; The Hollander agitator; Shallow pyramid refiner; Middle pyramid refiner; The wide-angle conical refiner; The table roller refiner; Two disk refiners and many disks refiner.
12. according to the method for the claims any one, wherein during one of bleaching stage that chemistry, machinery or recycled pulps are processed, catalyst and hydrogen peroxide are added in paper pulp.
13. method is according to claim 12 wherein added catalyst and hydrogen peroxide in the paper pulp in equipment, described equipment is selected from the paper pulp blender; Bleaching tower; Paper pulp is detained pipe; Washer; The paper pulp storage tower; Boiling blender and pulper.
14. according to claim 1 to 11 any one method, wherein paper pulp fiber stands bleaching stage in advance.
15. according to the method for the claims any one, the solution that wherein contains catalyst and hydrogen peroxide comprises the organic sequestering agent of 0.01-50kg/ ton oven dry paper pulp, this chelating agent is selected from: aminophosphonic acid chelating agent and carboxylic acid chelating agent.
16. method according to claim 15, wherein chelating agent is selected from: diethylenetriamines five (methylene phosphonic acid sodium salt), MGDA (MDGA), GLDA (glutamic acid oxalic acid), IDS (iminodisuccinic acid), EDDS (EDDS), EDTA (ethylenediamino tetraacetic acid) and DTPA (DTPA).
17. according to the method for the claims any one, wherein monitoring is input to the energy of refinement treatment, and based on energy input threshold value, paper pulp is processed into paper, paper handkerchief or cardboard.
18.pH be that the aqueous solution of the manganese transition-metal catalyst of 6-13 and hydrogen peroxide is for increasing the purposes of the increase degree of freedom value in subtractive process of cellulosic pulp fibers, wherein the manganese transition-metal catalyst is pre-formed monokaryon Mn (II), Mn (III), Mn (IV) or double-core Mn (II) Mn (II), Mn (II) Mn (III), Mn (III) Mn (III), Mn (III) Mn (IV) or Mn (IV) Mn (IV) transition-metal catalyst, the part of transition-metal catalyst is formula (I):
Figure FPA00001673723100031
Wherein:
Figure FPA00001673723100032
P is 3;
R independently is selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl;
R 1, R 2, R 3And R 4Independently be selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
19. the purposes of claim 18, wherein said purposes are included in the method that claim 1-17 any one limits.
20. method that can be by according to claim 1-17 any one or by according to claim 18 or the purposes of claim 19 paper, paper handkerchief or the cardboard that obtain.
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