CN103109015B - The freedom of paper product - Google Patents

The freedom of paper product Download PDF

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Publication number
CN103109015B
CN103109015B CN201180037116.7A CN201180037116A CN103109015B CN 103109015 B CN103109015 B CN 103109015B CN 201180037116 A CN201180037116 A CN 201180037116A CN 103109015 B CN103109015 B CN 103109015B
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China
Prior art keywords
pulp
paper pulp
paper
hydrogen peroxide
catalyst
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Expired - Fee Related
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CN201180037116.7A
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Chinese (zh)
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CN103109015A (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 with catalyst and the condition optimizing of hydrogen peroxide treatment paper pulp, to produce the energy reduction that Freeness value (SR) makes to need in the mechanical agitation of paper pulp in the web in the pulp production processed.

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) manufacturing paper, napkin (tissue), cardboard (board) or Related product can be obtained by the cellulose from timber and other source (such as Fructus Cannabis, Caulis et Folium Oryzae, Cotton Gossypii).Most raw materials are wood pulp, and it can be cork raw material or hardwood raw material.Cork fibrous carries coniferous tree such as pinaster, PiceameyeriRehd. Et Wils., alpine fir, the Pseudotsuga menziesii (Mirbel) Franco of pin.Hardwood fiber is from various types of deciduous trees such as Betula, Eucalyptus and acacia.Mechanical pulp contains major part initial wood mass element, and major part lignin is removed in chemical pulp.
Difference difference between cork (SW) and hardwood (HW) is the rigidity/conquassation of the length of individual fibers cellulose fiber of timber, the roughening of fiber and fiber.
Hardwood and cork must be subjected to concrete mechanical treatment (refining) so that wood conversion is the fibre pulp for forming paper web.The fiber of cellulose pulp suspensions through mechanical treatment with change fiber character.Cellulose pulp suspensions is processed into product, described product is compared with initial cellulose pulp suspensions, and the paper/napkin with freedom (Shopper-Riegler) value, the fineness of increase and the improvement of the stretching/tearing strength character of increase, increase manufactures character.The Freeness value increased causes the water separation capability that the paper/napkin reduced manufactures, the energy needed for which increasing dry paper the paper production speeds that can slow down.On the other hand, too low freedom produces paper/napkin firm not.The refined character to both chemical pulp and mechanical pulp has importance.In addition to dehydration, should also be noted that energy expenditure is high during subtractive process.
By regulating the chemical method of cellulose fibre with iron salt and hydrogen peroxide treatment fiber disclosed in WO2005/028744；Processing of Kraft softwood pulp produces the fibre property similar with hardwood fiber.
WO2004/022842 discloses by the method reducing energy of refiner mechanical pulp after pectinase treatment, has the paper pulp of specific freedom character with production.
EP0458397 discloses use manganese Isosorbide-5-Nitrae, 7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane (Me3-TACN) complex is as bleaching and oxidation catalyst, and it is used for textile and the purposes of dioxde pulp bleaching process.
U. S. application 2001/0025695A1, Patt etc. disclose use 1,2-pair-(4,7-dimethyl-Isosorbide-5-Nitrae, 7-tri-azacyclo-nonyl-1-yl)-ethane (Me4-DTNE) and Me3The ClO of the manganese complex of-TACN4 -And PF6 -Salt is respectively used to wood pulp delignification and bleaching.Comprise Me in use simultaneously4During the manganese compound of-DTNE, report does not has viscosity loss or viscosity loss little；Me is comprised in use3During the manganese compound of-TACN, viscosity loss is much bigger.Known have more low viscous cellulose and obtain the paper (PulpBleaching, PrincipleandPractice (association with pulp bleaching principle and put into practice) that intensity reduces, and C.W.Dence, D.W.Reeve edit, Tappi, Atlanta, and 1996).
WO2007/125517 discloses use 1,2-pair-(4,7-dimethyl-Isosorbide-5-Nitrae, 7-tri-azacyclo-nonyl-1-yl)-ethane (Me4-DTNE) and Me3-TACN is used for bleached cellulose substrate with buffer agent and chelating agen.
WO2008/086937 discloses use 1,2-pair-(4,7-dimethyl-Isosorbide-5-Nitrae, 7-tri-azacyclo-nonyl-1-yl)-ethane (Me4-DTNE) and Me3-TACN is used for bleached cellulose substrate, keeps pH constant simultaneously.
US2002/0066542A1 describes transition metal (particularly cobalt) complex of multidentate ligand, and the purposes that this compounds is in delignification and method for bleaching.With comprising Me3The reference experiments that the manganese complex of-TACN is carried out shows significant viscosity loss, and other compound described does not shows significant viscosity B coefficent.
Expecting to provide the method allowing paper/napkin Producer to use the subtractive process with reduced levels freedom, described method is produced and the identical pulp strength character generally provided by mechanical means.
Summary of the invention
It was found that improve the effect of these fibers refined with the transition metal complex of preformed aza-cyclic molecule and hydrogen peroxide treatment cellulose fibre.Process can be before, during or after subtractive process, generally before subtractive process or period is carried out.The refined character improved can be observed with the tensile strength properties of increase under identical Shopper-Riegler value (SR) by inputting in same mechanical.
Although it addition, extensively recognize that in paper pulp/paper field significantly reducing for Papermaking Properties of cellulose viscosity loss is less desirable, and comprising Me3The use of the Mn catalyst of-TACN produces significant viscosity loss, according to different research, has been surprisingly found that especially, and the use of this kind of catalyst causes subtractive process for the improvement of the effect of fibre property.
Present invention can apply to chemical pulp and mechanical pulp, including recycled pulps, be used for producing paper, napkin or cardboard.
We have found that energy expenditure and the time of formation cellulose pulp suspensions can reduce under the Mn catalyst effect together with hydrogen peroxide, described cellulose pulp suspensions can be further processed into having the paper improving freedom.
nullFirst aspect，The present invention provides the method processing cellulose pulp suspensions，It comprises the step of aqueous solution of (i) make cellulosic pulp fibers stand manganese transition-metal catalyst that pH is 6-13 and hydrogen peroxide，(ii) paper pulp is made to stand subtractive process until ShopperRiegler (SR) value reaches 10-90 °，And the paper pulp of generation is processed into paper、Napkin or cardboard，The concentration that wherein manganese transition-metal catalyst exists is that 0.0001-1kg/ ton dries paper pulp，And the concentration that hydrogen peroxide exists is that 0.1-100kg/ ton dries paper pulp，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):
Wherein:
P is 3；
R is independently selected from: on the N of another Q being connected to another ring by ethylene bridge in hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl or R.
R1、R2、R3And R4It is independently selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
Second aspect, manganese transition-metal catalyst that the present invention provides pH to be 6-13 and the aqueous solution of hydrogen peroxide are for increasing the purposes of the Freeness value of the cellulosic pulp fibers increase degree in subtractive process, wherein 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):
Wherein:
P is 3；
R is independently selected from: on the N of another Q being connected to another ring by ethylene bridge in hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl or R.
R1、R2、R3And R4It is independently selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
The specific embodiments of the first and second aspect according to the present invention, each R in formula (I) part is independently selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl.For these parts not bridged the most surprisingly, wherein, do not have on the N of another Q that R is connected to another ring by ethylene bridge to be suitable for using according to the inventive method, because prior art proves, carrying out delignification reaction with the transition-metal catalyst comprising this kind of part when, find that viscosity reduces.
On the other hand, the present invention provides paper, napkin or the cardboard that can be obtained by method according to a first aspect of the present invention or purposes according to a second aspect of the present invention.
Freeness value (SR) is the canonical measure value measured by ShopperRiegler method such as DrainabilityNORMENISO5267-1；Measure by this method for Freeness value (SR) herein.
Time needed for paper pulp refinement treatment will be had an impact by the concentration of catalyst and hydrogen peroxide, as the ratio of pulp quality and the amount of the activating agent of use.In this, for optimal conditions, the variable of surfactant concentration, temperature, pH and time is changeable variable.
It is preferably 1 minute-4 hours with catalyst and hydrogen peroxide to the process time of paper pulp, more preferably 5 minutes-3 hours, and most preferably 10 minutes-2 hours.Further, the temperature of the process that catalyst and hydrogen peroxide are preferably used is 30-95 DEG C, more preferably 40-90 DEG C.The pH using the process of catalyst and hydrogen peroxide is preferably pH8-12.
Transition metal complex and hydrogen peroxide can add at conventional bleaching stages.Or, transition metal complex and hydrogen peroxide such as can add in one or more delignifications and bleaching stage in the paper pulp (i.e. chemical pulp) of bleaching before refining stage or period adds.The chemical pulp so processed can be by contacting and delignification/bleaching (such as being defined according to the present invention) with hydrogen peroxide and transition-metal catalyst.Or, chemical pulp can be bleached (such as using ozone, chlorine dioxide) additionally by the non-catalytic of such as paper pulp or produce with the bleaching of hydrogen peroxide non-catalytic.
Or, Mn catalyst together with hydrogen peroxide all can at bleaching stage, also have after bleaching stage, before refining stage or period use.
Mechanical pulp and recycled pulps are processed, often carries out bleaching stage (such as relating to the use of hydrogen peroxide).In the case, may also include the manganese transition-metal catalyst according to first and second aspect of the present invention definition.Sometimes, the reproducibility blanching step of dithionite can be used to process recycled pulps (for this blanching step without manganese transition-metal catalyst).Or, manganese transition-metal catalyst and hydrogen peroxide can be used for processing mechanical pulp and recycled pulps, especially before machine finish process or period, at it with hydrogen peroxide and/or after bleaching with dithionite.
Or, Mn catalyst all can be at bleaching stage together with hydrogen peroxide, and again after bleaching stage, before refining stage or period uses.
These probabilities are being discussed in further detail below.Between transition-metal catalyst and the interpolation of hydrogen peroxide and subtractive process (if the former was carried out before the latter), the most necessarily carry out washing step.
It should be understood that the amount of transition-metal catalyst/hydrogen peroxide that paper pulp per ton (drying) needs is mainly mol ratio, but in the work weight commonly used in the trade amount of expression.In this, the transition-metal catalyst that paper pulp per ton (drying) needs, in the range of the scope of 0.0001-1kg/ ton paper pulp (drying), this equates about 0.1-1500mmol/ ton paper pulp (drying).According to specific embodiments of the present invention, the existence concentration of transition metal is in the range of 0.0005-0.2kg/ ton paper pulp (drying).The hydrogen peroxide (100%) of paper pulp per ton (drying) in the range of 0.1-100kg, more preferably 0.5-50kg, most preferably 1-30kg.Such as, the scope of the hydrogen peroxide (100%) of paper pulp per ton (drying) can be 0.1-25kg/ ton paper pulp (drying).It should be understood that the concentration range of each transition-metal catalyst disclosed herein can combine with the scope of each hydrogen peroxide disclosed herein.Such as, according to certain embodiments of the present invention, the existence concentration of transition-metal catalyst is in the range of 0.0005-0.2kg/ ton paper pulp (drying), and hydrogen peroxide (100%) scope of paper pulp per ton (drying) is 0.1-25kg.
Transition-metal catalyst: the preferred scope of the mol ratio of hydrogen peroxide is 1: 100-1: 10000.
Remember above content, be then conventional below for those skilled in the art: determine that condition is to produce Freeness value (SR) and to apply this condition industrially to have the paper pulp of desired Freeness value (SR) to web to obtain and to optimize by repetition test.
Detailed Description Of The Invention
By in the incoming pulp material of production Paper or cardboard grade to paper machine, it forms paper web and in the paper machine by pressurizeing and being dried therefrom except water.Water is removed by the power that is forced through paper.Once water is forced to leave from paper, collects water with felt.When with hand-made papermaking, use oil suction paper.The most pressurized and be dehydrated and be dried, to keep suitable absorbance and smoothness character for manufacturing the paper pulp of napkin or kitchen toilet paper grade.
Be dried be directed to use with air and or heat with from paper remove water.At the initial stage of papermaking, this realizes by being hung up as laundry by paper.Relatively modern when, use various forms of heat drying apparatus.On a papermaking machine, it is most commonly that steam-heated drying chamber.These drying machines can be heated to above the temperature of 200 (93 DEG C) and use in more than the long sequence of 40 tanks.Easily paper can be dried to less than 6% moisture with these heats produced.
There is concrete program to produce tissue.With reference to PaperandBoardGrades (paper and board grades), Book18, the 4th chapter, FinnishPaperEngineers ' AssociationandTAPPI (2000).
We have found that and change the paper pulp extent of reaction (being measured by its Freeness value (Shopper-Riegler-SR)) to machine finish process, the web manufactured by cellulose pulp suspensions with production with manganese transition-metal catalyst and hydrogen peroxide treatment cellulose pulp suspensions.By Mn catalyst process can before machine finish, period or carry out after machine finish process.Such as, and as discussed below, catalyst/hydrogen peroxide can add in pulp blend or paper pulp storage pool after machine finish, and wherein paper pulp can be stored before dehydration.
Ratio between hot strength and freedom be worth to improve, i.e. under identical Freeness value intensity increase or under relatively low Freeness value intensity identical.The optimal Freeness value of final products is obtained by monitoring treatment conditions.Further, under identical refining, can reach the volume of increase, to tissue particular importance.
We have found that and process cellulose pulp suspensions and monitoring concentration and the optimal Freeness value of the variable of time permission different periods.
Paper pulp dried in term is that paper pulp is dried at 100-105 DEG C with the paper pulp obtaining constant weight.With reference to TAPPI-test T240om-93 (1993).
Refined
Different types of equipment is usually used in mechanical treatment cellulose pulp.Agitator (including Hollander agitator) uses in many factories, but is replaced by conical refiner and disk refiner (can run in continuous process) the most in a large number.Conical refiner includes shallow angle refiner (Jordan), middle angle refiner (Conflo) and Radix Rumicis refiner (Claflin).Disk refines unit and comprises three types: table roller, double-arc spline, many disks refiner.
Refine and can carry out under low denseness (2-6%), medium consistency (10-20%) or high-consistency (30-35%).Depend on the demand of final products, different selections can be made for optimal denseness processing.With reference to PaperandBoardGrades (paper and board grades), PapermakingPart1.StockPreparationandWetEnd (preparation of papermaking part 1. raw material and green end), Book18,4th chapter, FinnishPaperEngineers ' AssociationandTAPPI (2000).
Processing can be to be mode in batches or continuously, because cost reason and quality control are easier to, and often preferred the latter.
Under many circumstances, different types of wood pulp such as softwood pulp and bardwood pulp are mixed.Either or both of which can independently refine.More refiner is often used in series, to strengthen benefit/energy requirement to process paper pulp.
Refining and can carry out chemical pulp, mechanical pulp and recycled pulps, these are all the objects of the present invention.
Depend on application, the refined of varying level can be carried out.For napkin and kitchen toilet paper grade, carry out low refined, to guarantee good volume, pliability, absorbance and brightness.Low refining is of value to above character, but has negatively affected intensity property.Therefore, wet strength agent and/or dry strength agent are often added.After refined, often obtain the Shopper-Riegler value of 10-30 °.
It is key parameter for printing paper and writing paper, impressionability and machinery performability.Paper must be clean and bright, has suitable slickness, compressibility, leaching ink ability and enough intensity for printing operation.Minimum opacity is another key character.Therefore, these paper needs good refined control to produce internal bond strength and to obtain correct smoothness and constitutive levels for its final use.Bleached paperboard grade (it is used for packing frozen food and liquid, and for cardboard and dixie cup) need good rigidity and volume and suitable slickness and impressionability.Internal combustion, wrinkle resistance and dimensional stability are also key factors.Therefore also need to the most refined to obtain these character (and the most too much reducing volume and rigidity).These application generally require the Shopper-Riegler value after 15-50 ° refined.
Fine and close paper needs the refined of significant quantity, depends on specific products needs.Release-base paper, cellophane and greaseproof all need the balance refining to obtain desired intensity and appearance characteristics widely.If especially purpose is intended to manufacture cellophane, subtractive process needs substantial amounts of energy requirement.The SR value of up to 90 ° can be needed.
Mechanical pulp generally requires refined to produce the Paper or cardboard material presenting suitable physical character.When refiner mechanical pulp, often reach the Shopper-Riegler value of 20-80 °.
Refined degree can on-line monitoring.Energy input is to determine the refined most important parameter of degree.There is control system and with on-line monitoring subtractive process and energy input is adjusted as desired.Probe monitoring refiner load, variations in temperature, flowing/denseness, draining/freedom (SR) etc..Main state-variable includes temperature, pH, denseness, additive, pretreatment, productivity ratio and applying energy.
By Mn catalyst and hydrogen peroxide treatment cellulose fibre
Application Mn catalyst and hydrogen peroxide treatment cellulose fibre can be carried out in the different phase during fiber treatment/paper-making process.This can be before machine finish process, during machine finish process or after machine finish process, generally before machine finish process or period.
In one or more delignifications and bleaching stage, the paper pulp of bleaching, chemical pulp can be used for processing further to produce napkin, Paper or cardboard the most.But, within the scope of the present invention, it be also possible to use the paper pulp (mechanical pulp) containing lignin or recirculation wood pulp.For integrated factory, bring wet pulp serosity into paper mill.When paper Producer obtains paper pulp from other factory, first pulpboard put in pond and decompose to obtain the pulp slurry being processed further of dilution.
In pulp mill, chemical pulp typically passes through hydrogen peroxide and/or uses other bleaching of such as ozone or chlorine dioxide to bleach.Mechanical pulp and recycled pulps often use hydrogen peroxide bleaching to increase brightness of pulp.During these bleaching stages one or more, the cellulose that hydrogen peroxide can process with acquisition in subtractive process can be used together with Mn catalyst.Mn catalyst and hydrogen peroxide can add during the different phase of pulp mill.
In paper pulp blender, chemicals is added in paper pulp, subsequently it is thoroughly mixed very much.Within the scope of the present invention, catalyst and hydrogen peroxide can be added in paper pulp blender to complete pulp processing.This can be carried out in low denseness blender (continuous print mixer, tower blender, dynamic mixer or static mixer), medium consistency blender (bolt blender, high-shear mixer) or high-consistency blender (including Kneader and collar plate shape blender).In steaming and decocting blender, steam is added in paper pulp to increase pulp temperatures.Also catalyst and hydrogen peroxide can be added in the paper pulp of steaming and decocting blender.
With reference to PulpBleaching, PrincipleandPractice (association with pulp bleaching principle and put into practice), C.W.Dence, D.W.Reeve edit, Tappi, Atlanta, and 1996, infra).
After adding association with pulp bleaching chemicals in a mixer, major part association with pulp bleaching is carried out in bleaching tower, washing pulp thereafter.Because bleaching process the slowest (typically 2-4 hour), bleaching tower trends towards greatly.But, the most also use less paper pulp to be detained pipe to allow some bleaching or to process reaction generation.Because process is usually continuous print, paper pulp upwards (upflow tower), downwards (downflow tower) or slowly move under a combination thereof (upstream-downflow tower).Within the scope of the present invention, can much shorter by catalyst and hydrogen peroxide treatment, it is allowed to relatively small treating column.
In washer, generally it is rinsed with the paper pulp of chemical treatments in the previous stage of processing procedure.Such as, acid chlorine dioxide NaOH solution is washed, to remove the solvable lignin residue of alkali and to 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 to use catalyst treatment paper pulp.
Paper pulp storage tower is designed to store paper pulp to be processed further over time.Usual this kind of storage tower before carrying out the process in association with pulp bleaching stage, or after final bleaching stage, can find before being such as transported to paper mill.Catalyst and hydrogen peroxide can add together with entering the paper pulp of this storage tower, it is allowed to the slow processing procedure of paper pulp.
Pulper is used for diluting waste paper (de inked pulp) and adding the bleaching for de inked pulp of alkali and hydrogen peroxide.Mn catalyst can be added in this pulper, to allow by catalyst treatment de inked pulp.
Mn catalyst and hydrogen peroxide also can add in cellulose pulp before the subtractive process in paper mill, such as homogenized in pond at pulper, high-density paper stock tank, paper pulp eliminating potential pool, paper pulp mixing pit or paper pulp.Pulper and high density pond are usually used in then mixing with water by adding water and dry raw material, semi-finished product and recyclable papers being prepared as pumpable state.In paper pulp mixing pit, two or more different types of paper pulp (optionally through refined) are made to mix and store to be processed further, such as softwood pulp and bardwood pulp.In homogenizing pond, the denseness of wood pulp is reduced to aspiration level.
Mechanical pulp often processes to process the fiber of distortion (twist together, crimp or spiral) in eliminating potential pool.Generally mechanical pulp is diluted to the denseness of 1-2%, is heated to 70-90 DEG C, stirs at least 20 minutes, be hereafter processed further.Being similar to the storage of above-mentioned paper pulp, paper pulp storage pool is used for storing wood pulp.Other above-mentioned pond is also commonly used for storing wood pulp and guaranteeing that the steady flow of paper pulp is processed in following process.Wood pulp can be delivered from association with pulp bleaching factory, or it can (integrated factory) produce on the spot.
Or catalyst/hydrogen peroxide can added before pulp refiner and allow during subtractive process with fibrin reaction.Owing in refined period heat release, or not existing reduction for being obtained the other energy requirement of optimization process effect by catalyst.Can use different purification apparatus, it includes agitator；Hollander agitator；Shallow angle conical refiner；Middle pyramid refiner；Radix Rumicis conical refiner；Table roller refiner；Double-arc spline refiner；Many disks refiner.With reference to PaperandBoardGrades (paper and board grades), PapermakingPart1.StockPreparationandWetEnd (preparation of papermaking part 1. raw material and green end), Book18,4th chapter, FinnishPaperEngineers ' AssociationandTAPPI (2000) and C.F.Baker, TappiJournal, 78,147,1995.
Finally, catalyst/hydrogen peroxide can add after the machine finish stage, such as in paper pulp is blended pond (wherein by different wood pulp source mixing) or paper pulp storage pool.Such as mechanical pulp can so process.
Or, Mn catalyst all can be at bleaching stage together with hydrogen peroxide, and again after bleaching stage, before refining stage or period uses.
Transition-metal catalyst
The manganese transition-metal catalyst used can be by using counter ion such as PF6 -Or ClO4 -And it is nondeliquescent.But, for industrial substrates, preferably transition metal complex is water miscible.The most preformed transition metal is that the form of salt makes its water solublity be at least 30g/l, such as at least 50g/l at 20 DEG C.Preferably salt is those in chloride, acetate, sulfate and nitrate.These salt are described in WO2006/125517.
According to specific embodiments of the present invention, each R in formula (I) part is independently selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH and pyridine-2-ylmethyl.According to specific embodiment, R is independently selected from: hydrogen, CH3, C2H5, CH2CH2OH and CH2COOH.
Preferably, R1、R2、R3And R4It is independently selected from: H and Me.
According to specific embodiment, R, R1、R2、R3And R4It is independently selected from: H and Me.Most preferably, catalyst source is in Isosorbide-5-Nitrae, 7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane (Me3-TACN)。
Preformed transition-metal catalyst salt preferably has at least one O2-The double-core Mn (III) of bridge or Mn (IV) complex.According to certain embodiments of the present invention, transition-metal catalyst can be complex [Mn (IV)2(μ-O)3(Me3TACN)2]2+Salt, than salt described above.
The application level of Mn catalyst can change with application, but usually 0.0005-0.2kg/t dries paper pulp (o.d.p.).
Hydrogen peroxide
Hydrogen peroxide is as aqueous solution itself, or as peroxy salt, such as percarbonate etc. provide.But, for cost reasons, preferably liquid hydroperoxide.The level preferably applying hydrogen peroxide is: 0.1kg/t-100kg/t dries paper pulp (o.d.p.), more preferably 0.3-50kg/to.d.p. most preferably 0.5-25kg/to.d.p.
Reagent preferably provides (pH is that 8-13 is optimal) with alkaline medium, and its alkalescence is preferably provided by sodium hydroxide or sodium carbonate.
The temperature of processing procedure is preferably 30 DEG C-95 DEG C, more preferably 40 DEG C-90 DEG C.
The process time using catalyst and hydrogen peroxide is 1 minute-4 hours, more preferably 5 minutes-3 hours, and most preferably 10 minutes-2 hours.
Chelating agen
Many chelating agen are suitable for the present invention and use.Example includes amino phosphonates do and carboxy acid salt chelator, such as amino phosphonates do and aminocarboxylate chelators.Suitably chelating agen includes edetate (EDTA), polyphosphonate such as DequestTMWith non-phosphate stabilisers such as EDDS (EDDS).
Aminocarboxylate chelators preferred with the chelating agen that Mn catalyst and hydrogen peroxide are used together or its mixture in processing step.It is below the example of preferred aminocarboxylate chelators: ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylenediamine tetracetic acid (HEDTA), iminodisuccinic acid (IDS), nitrilotriacetic acid(NTA) (NTA), N-Hydroxy-ethylamino oxalic acid, diethylene-triamine pentaacetic acid (DTPA), MDGA (MGDA), EDDS (EDDS) and alanine-N, N-oxalic acid.Most preferably aminocarboxylate chelators is diethylene-triamine pentaacetic acid (DTPA).
It is used as phosphine acid salt chelator；Preferably phosphine acid salt chelator is Dequest2066 (diethylenetriamines five (methylene phosphonic acid sodium salt).
When should be understood that use, chelating agen can be presented in free acid or salt.Such as, in a salt form in the presence of, it can be alkali metal, alkaline-earth metal, ammonium or substituted ammonium salt.Generally, chelating agen (if present) is in the form of its free acid or is sodium salt, potassium salt or magnesium salt.One example of the sodium salt of aminocarboxylate chelators is the five sodium-salt of diethylene triamine penta(methylene phosphonic acid), and market can have been bought by the trade mark of Dequest2066A.
In the solution containing Mn catalyst and hydrogen peroxide, the most preferred concentration of the chelating agen used in described method is that 0.01-50kg/ ton dries paper pulp, and most preferably 0.03-20kg/ ton dries paper pulp.
Experiment
Experiment 1: with or without [Mn2(μ-O)3(Me3TACN)2](CH3COO)2Hydrogen peroxide process softwood pulp (Me at pH11.03-TACN=1,4,7-trimethyls-Isosorbide-5-Nitrae, 7-7-triazacyclononane).
As other places (WO2006/125517) is open, it is thus achieved that [Mn2(μ-O)3(Me3TACN)2](CH3COO)2(being the aqueous solution of 3.5%).
The softwood pulp that initial ISO-brightness is 49.9 is handled as follows: add 10kg/odtpH to polyethylene (PE) bottle drying paper pulp of 10% denseness containing 250g2O2(odtp=drying ton paper pulp-equal to 29.4mMH2O2) and 7.2kg/odtpNaOH (equal to 18mMNaOH).Depend on experiment, add 0.04kg/odtp [Mn2(μ-O)3(Me3TACN)2](CH3COO)2(equal to 6.5 μMs of [Mn2(μ-O)3(Me3TACN)2](CH3COO)2) and 1.0kg/odtpDTPA (diethylene-triamine pentaacetic acid, five sodium-salt)-(exAkzoNobel；Trade mark DissolvineD50；Purity is 50%).Initial pH value is pH11.0 (measuring at 20 DEG C).
Note 1: this softwood pulp is at O2Delignification in-delignification step, and partly pass through ClO further2Step is bleached.
Note 2: it practice, the paper pulp used contains the dry of 35.6% and the water (dry content of 35.6%) of 64.4%.So 702.3g ' is wet ' paper pulp is for each experiment.
Note 3: all experiments are carried out under the denseness of 10%.
PE bottle is put into 1 hour and vibration in bleaching process in the water-bath (62.5 DEG C) of preheating.Subsequently pulp mixture is passed through filtered on buchner funnel and washs with substantial amounts of demineralised water.Use filtrate, measure H2O2Consumption.Bleached pulp is carried out by analysis below: kappa value, brightness and intrinsic viscosity.
Experimental result is given in Table 1.
Table 1 is used at 60 DEG C at initial pH11.0
[Mn2(μ-O)3(Me3TACN)2](CH3COO)2、
[Mn2(μ-O)3(Me3TACN)2](CH3COO)2With DTPA and need not
[Mn2(μ-O)3(Me3TACN)2](CH3COO)2Process the softwood pulp result of 60 minutes.
The long and that converges in table 1 shows [Mn2(μ-O)3(Me3TACN)2](CH3COO)2Add some effects that the bleaching of softwood pulp and kappa value are played, and the viscosity (degree that cellulose is polymerized) of softwood pulp had clearly act on.
The paper pulp processed is decomposed (DINENISO5263-1；2004-12), impact (PFI-grinding machine) (ENISO5264-2；2003-05) and experimental aqueous (Schopper-Riegler method,ENISO5267-1；2000-10).
Pass through Rapid-Method prepare laboratory handmade paper (ENISO5269-2；2005-04) and carry out the regulation (DINEN20187 of sample NC23/50；1993-11).Tests below uses handmade paper to carry out: grams (DINENISO536；1996-08), thickness, volume and density (DINENISO534；2005-05), air permeability (Bendtsen, ISO5636/3；1992-09), tension force, break-draw, hot strength, tensile figure, TEA and elastic modelling quantity (DINENISO1924-2；2009-05), internal bond strength (Z-direction, TAPPI541om-05；2005), breaking strength, tear index (EN21974；1994-09).
Result is given in the table below.
The condition that table 2 is given according to table 1 process after the impact of bleached softwood pulp and drainage result.
P1: without catalyst, without DTPA.
P2:[Mn2(μ-O)3(Me3TACN)2](CH3COO)2And DTPA
P3:[Mn2(μ-O)3(Me3TACN)2](CH3COO)2, without DTPA
Table 2 converges the long and and shows, presents similar SR value with catalyst with the pulp sample of hydrogen peroxide treatment until as 7000 turns of comparison, simultaneously when paper pulp refines under 9000 turns, it is thus achieved that the SR value of increase.
Table 3 uses intensity and the tear value of handmade paper prepared by as shown in table 2 refined under 5000 turns paper pulp.
Table 3 converges the long and and shows, hot strength, tensile energy absorption (TEA) and tensile index values, the breaking strength of reduction and the tear index increased with the pulp sample display that catalyst and hydrogen peroxide treatment are then refined in PFI grinding machine under 5000 turns, but other parameter is not significantly affected (all relative to the comparison-P1 without catalyst) by the process using catalyst and hydrogen peroxide.When catalyst is used in combination with DTPA, these tensile strength properties slightly strengthen.

Claims (19)

  1. null1. the method processing cellulose pulp suspensions，It comprises: step and (ii) of the aqueous solution of (i) make cellulosic pulp fibers stand manganese transition-metal catalyst that pH is 6-13 and hydrogen peroxide make paper pulp stand subtractive process until ShopperRiegler (SR) value reaches 10-90 °，And the paper pulp of generation is processed into paper、Napkin or cardboard，The concentration that wherein manganese transition-metal catalyst exists is that 0.0001-1kg/ ton dries paper pulp，And the concentration that hydrogen peroxide exists is that 0.1-100kg/ ton dries paper pulp，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):
    Wherein:
    P is 3；
    R is independently selected from: H, C1-C6-alkyl, C2OH、C1COOH and pyridine-2-ylmethyl；
    R1、R2、R3And R4It is independently selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy；
    Wherein catalyst and hydrogen peroxide being added in the paper pulp in equipment, described equipment is selected from: pulper；High-density paper stock tank；Washer；Paper pulp eliminating potential pool；Paper pulp homogenizes pond；Paper pulp mixing pit；Pulp refiner；Pulp dilution tank and paper pulp storage pool.
  2. Method the most according to claim 1, the concentration that wherein manganese transition-metal catalyst exists is that 0.0005-0.2kg/ ton dries paper pulp, and the concentration that hydrogen peroxide exists is that 0.1-25kg/ ton dries paper pulp.
  3. 3. according to the method for claim 1 or claim 2, wherein R is independently selected from: H, CH3、C2H5、CH2CH2OH and CH2COOH。
  4. Method the most according to claim 2, wherein R, R1、R2、R3And R4It is independently selected from: H and CH3。
  5. 5., according to the method for claim 1 or claim 2, wherein catalyst source is in Isosorbide-5-Nitrae, 7-trimethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane (Me3-TACN)。
  6. Method the most according to claim 4, wherein makes paper pulp stand subtractive process until ShopperRiegler (SR) value reaches 10-30 °, to produce tissue.
  7. Method the most according to claim 4, wherein makes paper pulp stand subtractive process until ShopperRiegler (SR) value reaches 15-50 °, to produce printing paper and writing paper.
  8. Method the most according to claim 4, wherein makes paper pulp stand subtractive process until ShopperRiegler (SR) value reaches 50-90 °, to produce trace paper and cellophane.
  9. Method the most according to claim 4, wherein makes mechanical pulp stand subtractive process until ShopperRiegler (SR) value reaches 20-80 °.
  10. Method the most according to claim 1, wherein pulp refiner is selected from: agitator；Hollander agitator；Shallow angle conical refiner；Middle pyramid refiner；Radix Rumicis conical refiner；Table roller refiner；Double-arc spline refiner and many disks refiner.
  11. 11. methods according to claim 1, one of bleaching stage wherein processed at chemistry, machinery or recycled pulps period, add to catalyst and hydrogen peroxide in paper pulp.
  12. 12. methods according to claim 11, wherein add to catalyst and hydrogen peroxide in the paper pulp in equipment, and described equipment is selected from paper pulp blender；Bleaching tower；Paper pulp is detained pipe；Washer；Paper pulp storage tower；Steaming and decocting blender and pulper.
  13. 13. methods according to claim 4, wherein paper pulp fiber is initially subjected to bleaching stage the most in advance.
  14. 14. methods according to claim 1, the solution wherein containing catalyst and hydrogen peroxide comprises the organic sequestering agent of 0.01-50kg/ ton drying paper pulp, and this chelating agen is selected from: amino phosphonates do chelating agen and carboxy acid salt chelator.
  15. 15. methods according to claim 14, wherein chelating agen is selected from: diethylenetriamines five (methylene phosphonic acid sodium salt), MGDA (MDGA salt), GLDA (glutamic acid diacetic acid salt), IDS (iminobisuccinate), EDDS (ethylenediamine disuccinate), EDTA (ethylenediamino tetraacetic acid salt) and DTPA (DTPA salt).
  16. 16. methods according to claim 1, wherein monitoring is input to the energy of refinement treatment, and based on energy input threshold value, paper pulp is processed into paper, napkin or cardboard.
  17. 17.pH is the manganese transition-metal catalyst of 6-13 and the aqueous solution of hydrogen peroxide for increasing the purposes of the Freeness value of the cellulosic pulp fibers increase degree in subtractive process, wherein 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, and the part of transition-metal catalyst is formula (I):
    Wherein:
    P is 3；
    R is independently selected from: H, C1-C6-alkyl, C2OH、C1COOH and pyridine-2-ylmethyl；
    R1、R2、R3And R4It is independently selected from: H, C1-C4-alkyl and C1-C4-alkyl hydroxy.
  18. The purposes of 18. claim 17, wherein said purposes is included in the method that any one of claim 1-16 limits.
  19. 19. can be by the method according to any one of claim 1-16 or the paper, napkin or the cardboard that are obtained by the purposes according to claim 17 or claim 18.
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