CN1300332A - A process for the production of paper - Google Patents

A process for the production of paper Download PDF

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Publication number
CN1300332A
CN1300332A CN99805548A CN99805548A CN1300332A CN 1300332 A CN1300332 A CN 1300332A CN 99805548 A CN99805548 A CN 99805548A CN 99805548 A CN99805548 A CN 99805548A CN 1300332 A CN1300332 A CN 1300332A
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suspension system
polymer
organic polymer
cationic organic
paper
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CN99805548A
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CN1155754C (en
Inventor
B·克莱米茨
H·霍尔斯特罗姆
A·阿斯普伦德
R·希卡
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Nouryon Chemicals International BV
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Akzo Nobel NV
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/08—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/01—Waste products, e.g. sludge
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/08—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH
    • D21H23/10—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH at least two kinds of compounds being added

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  • Paper (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The invention relates to a process for the production of paper from a suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension a drainage and retention aid comprising a cationic organic polymer, forming and dewatering the suspension on a wire, wherein the cationic organic polymer has an aromatic group and the suspension which is dewatered on the wire has a conductivity of at least 2.0 mS/cm. The invention further relates to a process for the production of paper from a suspension containing cellulosic fibres, and optional fillers, comprising adding to the suspension a drainage and retention aid comprising a cationic organic polymer having an aromatic group, forming and dewatering the suspension on a wire to obtain a wet web of paper and white water, recirculating the white water and optionally introducing fresh water to form a suspension containing cellulosic fibres, and optional fillers, to be dewatered, wherein the amount of fresh water introduced is less than 30 tons per ton of dry paper produced.

Description

The production method of paper
The present invention relates to papermaking, more specifically relate to the paper production method of the cationic organic polymer that in the papermaking paper stock, adds the band aromatic radical.The method can provide improved row's filter property and the property stayed.
In paper technology, be with the filler of cellulose fiber and selectivity use and aqueous suspension system (being referred to as paper stock) the feeding stuff box of additive, again paper stock is sprayed onto on the forming web from stuff box, by the water in the forming web eliminating paper stock, so just formed wet paper web on the net, paper web further dewaters and the dryer section in papermaking machine is carried out drying.The water that deckering obtains is called plain boiled water, and plain boiled water contains trickle particle (for example tiny fiber, filler and additive) usually, generally is to be recycled in the paper technology again.Be that filter aid and retention agent are added paper stock according to a conventional method,, they and fiber remained on together on the net so that promote leaching and strengthen the absorption of fine particle on cellulose fibre.Be widely used as filter aid and retention agent as cationic starch with based on the cationic organic polymer of cationic polymer of acrylamide etc.These polymer can use separately, but more often are used in combination with other polymer and/or anionic microparticles material (such as the silica of colloidal silica, colloidal aluminium modification and the anionic inorganic particle the bentonite).
US4,80,025; 5,368,833; 5,603,805; 5,607,552; 5,858,174 and WO97/18351 disclose in papermaking CATION and both sexes based on the use of the polymer of acrylamide and anionic inorganic particle as the paper stock additive.These additives are the most effective filter aid and the retention agents that use now.Similarly system is disclosed in EP-A805, in 234.
Yet observe, the performance that comprises the filter aid of cationic organic polymer and retention agent decays when using in the paper stock that high salt (being high-conductivity) and dissolving and material colloidal state are arranged.Usually requiring in this paper stock has the cationic polymer of high dose, but the row who obtains filter and stay the effect usually still can not be satisfactory.These problems have a large amount of recirculation plain boiled waters and only import in the paper mill of fresh water in a small amount in technology be very significant, further increased salt and colloidal materials thus in plain boiled water and the accumulation in the desire dehydration paper stock.
The present invention finds, in the paper stock that contains high salt (high conductivity) and colloidal materials and/or have the height whitewater closure paper technology in, use comprises the filter aid and the retention agent of the cationic organic polymer with aromatic radical, row's filter property that can be improved and the property stayed.More particularly, the present invention relates to the method for producing paper from the suspension system that contains the filler that cellulose fiber peacekeeping selectivity uses, be included in and add filter aid and retention agent, suspension system moulding on the net and the dehydration that comprises cationic organic polymer in the suspension system, the feature of this method is that cationic organic polymer has an aromatic radical, and desiring on the net, the electrical conductivity of the suspension system of dehydration is at least 2.0mS/cm.The present invention also relates to the method that above-mentioned feature is described, the further feature of this method is, it comprises suspension system moulding on the net and wet web or page and the plain boiled water of dehydration to obtain the cellulose fiber, plain boiled water recirculation is also optionally added the suspension system of fresh water with the filler of formation cellulose fiber and selectivity use, so that dehydration forms page.Wherein cationic organic polymer has an aromatic radical, and the fresh water amount of adding is less than the 30 tons/dried paper of producing per ton.Therefore the present invention relates to as the further method that limits in claims.
When therefore the present invention has the paper stock of high content of salt (and have high conductivity level) and colloidal materials in use, row's filter property that its result is improved and/or the property stayed.The present invention when being applied to a large amount of plain boiled water recirculation and a small amount of fresh water supply in the paper technology and/or use in the technology of fresh water of the high salt divalence or the polyvalent cation salt of (particularly as calcium salt and so on) content, the row's filter property that also is improved and/or the property stayed.Therefore, the present invention make the speed that improves papermaking machine and use than the additive of low dosage with arranged accordingly filter and/or stay effect to become possibility, thereby improve paper technology and economic benefit.
Cationic organic polymer (this paper also is referred to as " host polymer ") with aromatic radical of the present invention is the function with filter aid and retention agent." filter aid and retention agent " herein is meant one or more components (auxiliary agent, reagent or additive), when their add in paper stock, can obtain than do not add said one or more component better help filter property and/or the property stayed.Therefore host polymer provide improved help filter property and/or the property stayed, use separately or be used in combination no matter be with other one or more additional paper stock additives.Host polymer can be line style, branching or crosslinked for example microparticle material form.Preferred host polymer is water miscible or water dispersible.The aromatic radical of host polymer can be on main chain, the side group that perhaps preferably is connected in main chain or extends from main chain, or on the side group that is connected in main chain or extends from main chain.Fragrance (aryl) group that is fit to comprises that those contain the group of phenyl (optional replacement), phenylene (optional replacement) and naphthyl (optional replacement), for example have general formula-C 6H 5,-C 6H 4-,-C 6H -3-and-C 6H 2-group, for example with phenylene (C 6H 4-), xylylene (CH 2-C 6H 4-CH 2-), phenyl (C 6H 5), benzyl (CH 2-C 6H 5), phenethyl (CH 2-CH 2-C 6H 5) and substituted-phenyl (for example-C 6H 4-Y ,-C 6H 3-Y 2With-C 6H 2-Y 3) form, the one or more substituting groups (Y) that wherein are connected in phenyl ring can be selected from the alkyl of hydroxyl, halide (for example chloride), nitro and 1-4 carbon atom.
Host polymer can be selected from homopolymers and copolymer, and by one or more monomers preparations that comprise at least a monomer (suitable is ethylenically unsaturated monomer) that aromatic radical arranged and get, and suitable host polymer is the vinyl addition polymer." vinyl addition polymer " herein is meant that these monomers comprise by one or more vinyl monomers or the ethylenically unsaturated monomer polymer with the polyaddition reaction preparation: for example based on acrylamide with based on the monomer of acrylate.The host polymer that is fit to comprises the cationic ethylene based addition polymer, and it is with cationic monomer or comprises that the monomer mixture of the cationic monomer of representing with general formula (I) obtains through polymerization:
Figure 9980554800061
R in the formula 1Be H or CH 3R 2And R 3It preferably respectively is the alkyl of 1-3 (normally 1-2) carbon atom; A 1Be O or NH; B 1Be the alkylidene or the hydroxy propylidene of 2-8 (what be fit to is 2-4) carbon atom; Q is the substituent that contains aromatic radical (suitable is phenyl or substituted-phenyl), and it can be connected on the nitrogen with the alkylidene that 1-3 (what be fit to is 1-2) carbon atom arranged usually, and preferred Q is a benzyl; X-is the phase pair anion, is the halogen ion often, as chlorion.With general formula (I) is that the example of the monomer that is fit to of representative comprises with benzyl chloride and handles for example (methyl) acrylic acid dimethyl aminoethyl ester of (methyl) propenoic acid dialkyl aminoalkyl ester, (methyl) acrylic acid diethylamino ethyl ester and (methyl) acrylic acid dimethylamino hydroxypropyl ester, and dialkyl aminoalkyl (methyl) acrylamide, for example dimethyl aminoethyl (methyl) acrylamide, diethylamino ethyl (methyl) acrylamide, the quaternary ammonium type monomer that dimethylaminopropyl (methyl) acrylamide and diethylamino propyl group (methyl) acrylamide obtain.Preferred general formula (I) cationic monomer comprises acrylic acid dimethyl aminoethyl ester benzyl chloride quaternary ammonium salt and dimethylaminoethyl acrylate methyl base amino-ethyl ester benzyl chloride quaternary ammonium salt.
Host polymer can be have aromatic radical cationic monomer preparation homopolymers or include the cationic monomer of an aromatic radical and the copolymer of the monomer mixture preparation of one or more comonomers.The non-ionic co-monomers that is fit to comprises the monomer with general formula (II) representative:
Figure 9980554800071
R in the formula 4Be H or CH 3R 5And R 6Respectively for H or 1-6, what be fit to is 1-4, the alkyl of 1-2 carbon atom normally, suitable is alkyl; A 2Be O or NH; B 2Be 2-8, what be fit to is the alkylidene or the hydroxy propylidene of 2-4 carbon atom, perhaps another kind of possible, A and B do not exist and are a singly-bound (O=C-NR between C and N 5R 6).The example of such suitable copolymerisable monomer comprises (methyl) acrylamide; Monomer such as N-alkyl (methyl) acrylamide and N based on acrylamide, N-dialkyl group (methyl) acrylamide, for example, N-n-pro-pyl acrylamide, N-isopropyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, N-isobutyl group (methyl) acrylamide and the N-tert-butyl group (methyl) acrylamide; And dialkyl aminoalkyl (methyl) acrylamide, for example dimethyl aminoethyl (methyl) acrylamide, diethylamino ethyl (methyl) acrylamide, dimethylaminopropyl (methyl) acrylamide and diethylamino propyl group (methyl) acrylamide; Based on the monomer of acrylate as (methyl) propenoic acid dialkyl aminoalkyl ester, for example (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid tert-butyl group amino-ethyl ester and acrylic acid dimethylamino hydroxypropyl ester; And vinylamide, for example N-vinyl formamide and N-vinyl acetamide.Preferred non-ionic co-monomers comprises acrylamide and Methacrylamide, i.e. (methyl) acrylamide, and preferred host polymer is based on the polymer of acrylamide.
The cationic comonomer that is fit to comprises the monomer with general formula (III) representative:
Figure 9980554800081
R in the formula 7Be H or CH 3R 8, R 9And R 10Respectively for H or be preferably 1-3, the alkyl of 1-2 carbon atom normally, suitable is alkyl; A 3Be O or NH; B 3Be 2-4, what be fit to is the alkylidene or the hydroxy propylidene of 2-4 carbon atom; X -Be the phase pair anion, normally methylsulfuric acid radical ion or halogen ion such as chlorion.The example of the CATION copolymerisable monomer that is fit to comprises the acid-addition salts and the quaternary ammonium salt of above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester and dialkyl aminoalkyl (methyl) acrylamide, their preparation be with acid such as example hydrochloric acid, sulfuric acid or as the quaternizing agent of methyl chloride, dimethyl suflfate etc. prepare; And chlorination diallyl dimethyl ammonium.But preferred copolymerizable cationic monomers comprises (methyl) acrylic acid dimethyl aminoethyl METH chlorine quaternary ammonium salt and chlorination diallyl dimethyl ammonium.But the anionic monomer of copolymerization also can adopt as acrylic acid, methacrylic acid, various sulfonate vinyl addition monomers etc., and preferred use in a small amount.
Host polymer of the present invention can prepare from monomer mixture, monomer mixture generally comprise 1-99 mole %, suitable be the cationic monomer with aromatic radical (preferably with general formula (I) representative) of 2-50 mole %, preferred 5-20 mole % and 99-1 mole %, suitable be 98-50 mole %, preferred other comonomer that preferably comprises acrylamide or Methacrylamide ((methyl) acrylamide) of 95-80 mole %.What this monomer mixture was fit to is (methyl) acrylamide that comprises 98-50 mole %, preferred 95-80 mole %, and the summation of its percentage is 100.
One or more contain the polymer of the monomer of aromatic radical through the condensation reaction preparation the also optional freedom of host polymer.The example of this monomer comprises toluene di-isocyanate(TDI), bisphenol-A, phthalic acid, phthalic anhydride etc., and they can be used for the preparation of cation polyurethane, cationic polyamide-amine etc.
In addition, host polymer can be the polymer that carries out fragrant modification with the reagent that contains aromatic radical.Such suitable modifier comprises benzyl chloride, benzyl bromide a-bromotoluene, N-(3-chloro-2-hydroxypropyl)-N-benzyl-N, N-alkyl dimethyl ammonium chloride and N-(3-chloro-2-hydroxypropyl) pyridinium chloride.The suitable polymer of this fragrant modification comprises the vinyl addition polymer.If polymer contains the quaternised uncle's nitrogen of the agent that can be modified, using the common result of this reagent is that polymer is become is cationic.In addition, it can be cationic desiring by the polymer of fragrant modification, for example the cationic ethylene based addition polymer.
The common charge density of host polymer restrains dry polymeric at 0.1-6.0meqv/, and that suitable is 0.2-4.0, preferred 0.5-3.0.
The weight average molecular weight of synthetic host polymer normally is at least about 500,000, and what be fit to is about 1,000, and is preferred about 2,000 more than 000, more than 000.The upper limit is not a key issue, can be generally 30,000,000 about 50,000,000, and what be fit to is 25,000,000.
Host polymer of the present invention can be any coherent condition, such as solid form (for example powdery), liquid form (for example solution, emulsion, dispersion liquid comprise the salt dispersion liquid) etc.Be used for suitable host polymer example of the present invention and be included in the polymer that following document is narrated: US5,169,540; 5,708,071, EP-A183,466; 525,751 and 805,234, provide reference at this.What host polymer was fit to when adding paper stock is liquid form, for example the aqueous solution or aqueous dispersions form.
Host polymer can be added in the paper stock of desire dehydration, and its amount can change in a wide limit, and its amount depends mainly on paper stock type, salt content, salt type, filler content, filler type, adds point etc.In general, the addition of host polymer should obtain than there be not preferably the property stayed the added-time.The common addition of host polymer is at least 0.001%, usually is at least 0.005% (weight), calculates based on dried paper stock material.Its upper limit normally 3%, what be fit to is 1.5% (weight).
In a best specific embodiments of the present invention, host polymer is used in combination with an additional paper stock additive, thereby formed filter aid and the retention agent that comprises two or more components, be commonly referred to filter aid and retention agent, used term " filter aid and retention agent " is meant two or more components (auxiliary agent, reagent or additive), they after adding paper stock, obtain helping preferably when not adding these components filter property and the property stayed.The example of such suitable paper stock additive comprises the anionic microparticles material, for example anion organic granular and anionic inorganic particle, water soluble anion vinyl addition polymer, low molecular weight cationic organic polymer, aluminium compound and their combination.Aspect in this specific embodiments one was preferred, host polymer was used in combination with an anionic microparticles material, it should be noted that with anionic inorganic materials to be used in combination.In this specific embodiments on the other hand, host polymer is used in combination with an anionic inorganic particle and a low molecular weight cationic organic polymer.Aspect this specific embodiments another, host polymer is used in combination with an anionic inorganic particle and an aluminium compound.
The operable anionic inorganic particle of the present invention comprises silica-based particle of anion and smectite-type clay.The anionic inorganic granular size that is in the colloidal state scope is preferred.The silica-based particle of anion is promptly based on SiO 2Or the particle of silicic acid, be preferred the use, this particle is normally supplied with colloid aqueous dispersion (being so-called colloidal sol).The example of the silica-based particle that is fit to comprises colloidal silica and dissimilar poly-silicic acid.Silica-based colloidal sol also can modification and is contained other composition, for example aluminium and/or boron, and they can be present in water or the silica-based particle.The silica-based particle that is fit to of this type comprises colloidal aluminium modified silica and alumina silicate.The mixture of this suitable silica-based particle also is operable.The filter aid and the retention agent that comprise the suitable silica-based particle of anion are disclosed in the following document: US4,388,150; 4,927,498; 4,954,220; 4,961,825; 4,980,025; 5,127,994; 5,176,891; 5,368,833; 5,447,604; 5,470,435; 5,543,014; 5,571,494; 5,573,674; 5,584,966; 5,603,805; 5,688,482; 5,707,493.At this as a reference.
The average grain diameter of the silica-based particle of anion that is fit to below about 50nm, preferably below about 20nm, the scope of 1-10nm more preferably from about.Press the convention in the chemistry of silicones, particle diameter refers to the mean size of primary granule, and they can be that assemble or non-gathering.The specific area of the silica-based particle that is fit to is about 50m 2More than/the g, preferred 100m 2More than/the g.In general, specific area can reach about 1700m 2/ g, preferred 1000m 2/ g.Specific area can be measured with the NaOH titration by known method, for example, and Sears, " Analytical Chemistry (analytical chemistry) " 28, (1956): 12,1981-1983 and US5, the method described in 176,891.Resulting area is represented the average specific surface area of particle.
In a best specific embodiments of the present invention, the anionic inorganic particle is silica-based particle, and specific area is at 50-1000m 2/ g scope, preferred 100-950m 2/ g.The colloidal sol that the silica-based particle colloidal sols of these types also comprises modification is as the silica-based sols that contains aluminium and the silica-based sols of boracic.The S-value of the preferred silica base particle that exists in the colloidal sol is in the 8-45% scope, and preferred 10-30% contains the specific area scope at 300-1000m 2/ g, suitable be 550-950m 2/ g, preferred 750-950m 2The silica base particle of/g.These colloidal sols can come modification with aluminium and/or boron as above-mentioned.For example particle can carry out surface modification to the degree that has the 2-25% silicon atom to replace with aluminium.The mensuration of S-value and calculating are described in Iler and Dalton, J.Phys.Chem. (physical chemistry magazine) 60 (1956), 955-957.The S-value refers to the degree that aggregation extent or micro gel form, the lower higher aggregation extent of S-value indication.
In another best specific embodiments of the present invention, silica base particle is selected from high-specific surface area, and (that suitable is about 1000m 2More than/the g) poly-silicic acid and modified polysilicate.Its specific area can be at 1000-1700m 2/ g scope, preferred 1050-1600m 2/ g scope.Modified polysilicate colloidal sol can contain other composition, for example aluminium and/or boron, and they can be present in water or the silica-based particle.In present technique, poly-silicic acid is also referred to as polymeric silicicacid, poly-silicic acid micro gel, polysilicate and polysilicate micro gel, and they all are included among poly-silicic acid one speech used herein.The aluminum contained compound of this type generally is also referred to as poly-alumino-silicate and poly-alumino-silicate micro gel, and they all are included in colloidal aluminium modified silica one speech used herein and alumina silicate one speech.
The smectite-type clay of using in the method is known in the art in the present invention, and it comprises natural, synthetic and chemically treated material.The example of the smectite-type clay that is fit to comprises imvite/bentonite, hectorite, beidellite, nontronite and talcum powder.Behind the preferred bentonite, particularly swelling 400-800m is arranged preferably 2The bentonite of/g surface area.The clay that is fit to is disclosed in US4,753,710; In 5,071,512 and 5,607,552, provide reference at this.
Can be used for anion organic granular of the present invention and comprise high crosslinked anionic vinyl addition polymer, what be fit to is the copolymer that comprises the vinyl addition monomer of anionic monomer such as acrylic acid, methacrylic acid and sulfonation or phosphonic acidsization, normally with as non-ionic monomer copolymerization such as (methyl) acrylamide, (methyl) alkyl acrylates.Useful anion organic granular also comprises the anion condensation polymer, for example melamine-sulfonic acid colloidal sol.The water soluble anion vinyl addition polymer that can use in the present invention comprises the copolymer by anionic monomer such as acrylic acid, methacrylic acid and sulfonate vinyl addition monomer, normally with as non-ionic monomer copolymerization such as acrylamide, alkyl acrylates, for example at US5,098,520 and 5, disclosed in 185,062.Provide reference at this.
The low molecular weight that can use in the present invention (calling LMW in the following text) cationic organic polymer comprises that those are commonly referred to and are used as the polymer of anion refuse gathering agent (ATC).ATC is neutralizer and/or the fixative that conduct known in the art is present in the harmful anion material in the paper stock, and they are used in combination with filter aid and/or retention agent further improved help filter property and/or retention usually are provided.The LMW cationic organic polymer can obtain from natural or synthetic source, preferred LMW synthetic polymer.The suitable organic polymer of this type comprises the high electric charge cationic organic polymer of LMW, such as polyamine, polyamide-based amine, polyethylene imine based, based on the homopolymers and the copolymer of chlorination diallyl dimethyl ammonium, (methyl) acrylamide and (methyl) acrylate.About the molecular weight of host polymer, the LMW cationic organic polymer that preferred molecular weight is lower, suitable molecular weight is at least 2,000, and preferably at least 10,000.The molecular weight upper limit is about 700,000 usually, and what be fit to is about 500,000, and common about 200,000.
The aluminium compound that can use in the present invention comprises alum, aluminate, aluminium chloride, aluminum nitrate and many aluminium compounds, such as the many aluminium of many aluminium compounds, silicic acid-sulfuric acid and their mixture of the many aluminium of chlorination, the many aluminium of sulfuric acid, chloride ion-containing and sulfate ion.Many aluminium compounds also can contain other anion except that chlorion, for example the anion that obtains from phosphoric acid, sulfuric acid, organic acid such as citric acid and oxalic acid.
Filter aid of the present invention and retention agent component can add paper stock with any order in the usual way.When use comprised the filter aid of a host polymer and an anionic microparticles material (being apparent that the anionic inorganic particle) and retention agent, it was preferred adding host polymer before paper stock adds microparticle material, even can use opposite addition sequence.Shearing section (can select) preceding adding host polymer and add anion particle from pumping, mixing, cleaning etc. after section is further preferred.When using LMW cationic organic polymer or aluminium compound, such component adds paper stock before being preferably in and adding host polymer, optionally is used in combination with an anionic microparticles material.In addition, LMW cationic organic polymer and host polymer can be basically simultaneously respectively or mix the adding paper stock, US5 for example, disclosed method in 858,174 provides reference at this.LMW cationic organic polymer and host polymer preferably added paper stock before adding the anionic microparticles material.
The amount that filter aid of the present invention and retention agent add in the paper stock that will dewater can change in the scope of a broad, be decided by especially component type and number, paper stock type, salt content, salt type, filler content, filler type, add point, whitewater closure degree etc.In general, the amount that adds auxiliary agent should obtain better helping when not adding these components filter property and/or retention.The common addition of host polymer is at least 0.001%, often be at least 0.005% (weight), calculate based on dried paper stock material.Its upper limit normally 3%, what be fit to is 1.5% (weight).Similarly amount is suitable for water soluble anion vinyl addition polymer (as the words of using).When using the anionic microparticles material in technology, it adds total amount and is at least 0.001% (weight) usually, is at least 0.005% (weight) sometimes, calculates based on the paper stock dry.Its upper limit normally 1.0%, what be fit to is 0.6% (weight).When using anionic silica-based particles, its adding total amount that is fit to is calculated with SiO2 and based on the paper stock dry in 0.005-0.5% (weight) scope; Preferably measure in 0.01-0.2% (weight) scope.When using the LMW cationic organic polymer in technology, the amount that can add is at least 0.05%, calculates based on the paper stock dry that will dewater; The amount that is fit to is in the 0.07-0.5% scope, preferred 0.1-0.35% scope.When using aluminium compound in technology, the amount in the paper stock that adding will be dewatered is decided by the type of used aluminium compound and requires other effect of its generation.For example utilize the precipitating agent of aluminium compound as the abietyl sizing agent what know in the art; It adds total amount normally at least 0.05%, calculates with Al2O3 with based on the paper stock dry.The amount that is fit to is in the 0.5-3.0% scope, preferred 0.1-2.0% scope.
Method of the present invention is applicable to from suspension system produces paper, the filler that this suspension system cellulose fiber and selectivity are used, promptly it has high electric conductivity.Usually, the electrical conductivity of Tuo Shui paper stock is 2.0mS/cm at least on the net, suitable is 3.5mS/cm at least, preferred 5.0mS/cm at least, and 7.5mS/cm at least most preferably.Electrical conductivity available standards instrument is measured, for example the WTW LF 539 that provides of Christian Berner.What the mensuration of above-mentioned value was fit to is the electrical conductivity of measuring feeding or being present in the cellulose suspension system in the paper machine stuff box, or measures the electrical conductivity of the plain boiled water that obtains after the suspension system dehydration.High conductivity means high salt (electrolyte) content.That salt wherein can be based on is single-, the CATION such as the alkali metal of divalence and multivalence, for example Na +And K +Alkaline-earth metal, for example Ca 2+And Mg 2+Aluminium ion, for example Al 3+, Al (OH) 2+Many aluminium ions and single-, divalence and multivalent anions such as halogen ion, for example Cl -, sulfate radical, for example SO 2- 4, HSO 4 -Carbonate, for example CO 3 2-, HCO 3 -, silicate and rudimentary organic acid.The present invention is particularly useful in from the paper stock of the high content of salt that divalence and polyvalent cation are arranged and makes paper, common divalence and concentration of multivalent cations be at least 200ppm, suitable be 300ppm, preferred 400ppm at least at least.Salt can be from the stock preparation stage, promptly from forming the material of paper stock, for example water, cellulose fiber peacekeeping filler are particularly in large-scale paper mill, normally mix with water from the concentration of fibre aqueous suspension system that pulp mill comes, be suitable in the paper mill, producing paper to form rare suspension.Salt also can be from the various additives in the adding paper stock, from offering fresh water of this technology or the like.In addition, in the technology that a large amount of circulations of plain boiled water are arranged, salt content is normally higher, can cause salt to accumulate in a large number in the water circulation of technology like this.
The present invention further includes the paper technology that a large amount of recirculation of plain boiled water promptly have the height whitewater closure.For example produce one ton of dried paper and use 0-30 ton fresh water, paper per ton is less than 20 usually, be fit to be less than 15, preferably be less than 10, be to be less than 5 tons of fresh waters significantly.What the recirculation of the plain boiled water that obtains in this technology was fit to is to comprise that the filler that plain boiled water and cellulose fibre and/or selectivity are used mixes the suspension system that forms the needs dehydration, and preferably the suspension system of the filler that plain boiled water was used with cellulose fiber and selectivity before suspension system enters the forming web dehydration is mixed.Can with plain boiled water add filter aid and retention agent component (as using) before, among, simultaneously or afterwards, and before adding host polymer, simultaneously or mix with suspension system afterwards.Fresh water can add technology in any stage, for example can mix with cellulose fibre so that form suspension system; Can with paper stock with before plain boiled water mixes, simultaneously or afterwards, and add filter aid and retention agent component (if you are using) before, among, simultaneously or afterwards, and before the adding host polymer, simultaneously or mix with the suspension system of cellulose fiber afterwards, to be diluted to the suspension system that will dewater.
Other habitual in papermaking additive can certainly be used in combination with additive of the present invention, as dried reinforcing agent, wet reinforcing agent, optical brightener, dyestuff, sizing agent such as abietyl sizing agent and cellulose reactive sizing agent, for example ketene dimer and succinyl oxide or the like.Cellulose suspension system or paper stock also can contain mineral filler such as kaolin, potter's clay, titanium dioxide, gypsum, talcum and natural and synthetic calcium carbonate such as the chalk of general type, levigate marble and precipitated calcium carbonate.
Method of the present invention is the production that is used for paper." paper " used herein not only comprises paper and its goods certainly, also comprises thin slice or web-shaped product (such as plate and cardboard) and its goods of other cellulose fiber.Method of the present invention can be used for producing paper from the dissimilar suspension system of cellulose fiber, and suspension system should contain this fiber of at least 25%, preferably at least 50% (weight), calculates based on dry.Suspension system can be based on the fiber that paper pulp obtains that grinds from chemical pulp such as sulfate, sulphite and organic solvent paper pulp, mechanical pulp such as thermomechanical pulp, chemistry-thermomechanical pulp, refiner paper pulp and hardwood and cork, also can be based on regenerated fiber, use the paper pulp of de-oiling China ink and their mixture sometimes.
The present invention is existing to be further specified with following embodiment, but there is no the meaning that limits it.Unless otherwise noted, " part " and " % " is respectively weight portion and percetage by weight.
Embodiment 1 (contrast)
Row's filter assessment of performance working power row filter analyzer (DDA) (Sweden Akribi company provides).This instrument is on removing the another side of net that unstopper imposes on vacuum paper stock the time, and the paper stock of measuring fixed volume is got rid of the time of water by net.
Employed batching is based on bleaching birch/pine (60/40) sulphate pulp that is refined to 200 ℃ of SF of 70% (weight) and the levigate marble of 30% (weight).Stock volume is 800 milliliters, denseness 3%, and pH is about 8.
Adding sodium sulphate transfers to 0.47mS/cm with the electrical conductivity of paper stock.In whole test, paper stock speed with 1500rpm in the baffling jar is stirred, the adding of chemicals is following to be carried out: ⅰ) add cationic polymer in paper stock, then stirred for 30 seconds, ⅱ) in paper stock, add the anionic inorganic particle, then 15 seconds of stirring particles, ⅲ) leaching paper stock is noted down the leaching time simultaneously automatically.
The polymer that is used for experimental series is P1) cation copolymer for preparing with acrylamide (90 moles of %) and acryloxy ethyl dimethyl benzyl ammonium chloride (10 moles of %) polymerization, mean molecule quantity is about 6,000,000, P2) cation copolymer for preparing with acrylamide (90 moles of %) and acryloxy ethyl trimethyl ammonium chloride (10 moles of %) polymerization, mean molecule quantity is about 6,000, and 000.P1 and P2 is water-soluble, use with 0.1% aqueous solution.
Used anionic inorganic particle is a silica base particle, is US5, disclosed type in 368,833.The S-value of this colloidal sol is about 25%, contains specific area and is about 900m 2The silica granule of/g, the degree of carrying out surface modification with aluminium is 5%.The addition of silica-based particle is 1.0 kg/ton, with SiO 2And based on dried paper stock system computing.
Table 1 is depicted as the leaching time of the P1 and the P2 of various dose, with dry polymeric to dried paper stock system computing.
Table 1
Tested number Dose of polymer (kg/ton) SiO 2(kg/ton) Electrical conductivity (mS/cm) Dewatering time (second)
P1 P2
1 2 3 4 0 1 1.5 2 0 1 1 1 0.47 0.47 0.47 0.47 18.4 12.5 6.9 4.9 18.4 10.6 5.6 4.3
Embodiment 2 (contrast)
Dehydration is to evaluate with a DDA among the embodiment 1 and a nephelometer coupling with the property stayed.Primary the property stayed evaluation is to measure the filtrate that the leaching paper stock obtains and the turbidity of plain boiled water.
Used batching is based on the TMP/SGW paper pulp (80/20) of 56% (weight) peroxide bleaching, bleaching birch/pine sulphate pulp (60/40) and 30% (weight) potter's clay that 14% (weight) is refined to 200 ℃ of SF.In paper stock, add the colloidal state partial bleaching water that 40 grams per liters derive from the SC paper mill, filter, concentrate with the UF filter then, exceed with 200,000 by 5 μ m sieve.Stock volume is 800 milliliters, and denseness 0.14% transfers to 4.0 with dilute sulfuric acid with pH.Electrical conductivity is with adding calcium chloride (60ppmCa 2+), magnesium sulfate (18ppmMg 2+) and sodium bicarbonate (134ppm HCO 3 -) regulate.
Be used for this experimental series like the polymer of embodiment 1 and the anionic inorganic particulate species.Used the polymer of 1 kg/ton and two kinds of dosage of 2 kg/ton respectively, with dry polymeric to dried paper stock system computing.Table 2 be depicted as various dose silica base particle dehydration and stay effect, with SiO 2And based on dried paper stock system computing.
Table 2
Tested number Dose of polymer (kg/ton) ??SiO 2Dosage (kg/ton) Electrical conductivity (ms/cm) Dewatering time (second) Turbidity (NTU)
??P1 ??P2 ??P1 ??P2
????1 ????2 ????3 ????4 ????5 ????6 ????1 ????1 ????1 ????2 ????2 ????2 ????0 ????1 ????2 ????0 ????1 ????2 ????1.375 ????1.375 ????1.375 ????1.375 ????1.375 ????1.375 ?21.2 ?17.2 ?21.2 ?15.2 ????11 ?11.4 ?18.7 ?16.1 ?18.6 ?14.2 ?9.9 ?10.8 ?63 ?67 ?66 ?47 ?47 ?45 ?55 ?60 ?57 ?45 ?47 ?50
Embodiment 3
The dehydration of this experimental series is to evaluate with step used among the embodiment 2 with staying effect.
That uses among used batching and the embodiment 2 is identical.Stock volume is 800 milliliters, and pH is about 7.Electrical conductivity is adjusted with calcium chloride, therefore simulates the very high electrolyte content and the whitewater closure of high level.
Be used for this experimental series like polymer among the embodiment 1 and the anionic inorganic particulate species.
Table 3 be depicted as various dose silica base particle dehydration and stay effect, with SiO 2And based on dried paper stock system computing.
Table 3
Tested number Dose of polymer (kg/ton) SiO 2Dosage (kg/ton) Electrical conductivity (mS/cm) Dewatering time (second) Turbidity (NTU)
??P1 ??P2 ??P1 ????P3
????1 ????2 ????3 ????4 ????2 ????2 ????2 ????2 ????0 ????1 ????2 ????3 ??990ppm?Ca 2+????5.5 ????5.5 ????5.5 ????5.5 ????14.2 ????10.8 ????7.7 ????7.3 ??19.2 ??13.9 ??9.5 ??8.9 ????42 ????41 ????35 ????32 ????64 ????43 ????36 ????39
????5 ????6 ????7 ????8 ????2 ????2 ????2 ????2 ????0 ????1 ????2 ????3 ??1?300ppm?Ca 2+????7.0 ????7.0 ????7.0 ??16.2 ??10.0 ??7.5 ??7.7 ??23.0 ??17.1 ??13.6 ??11.7 ????46 ????40 ????36 ????34 ????50 ????45 ????44 ????44
????9 ????10 ????11 ????12 ????2 ????2 ????2 ????2 ????0 ????1 ????2 ????3 ??1930ppm?Ca 2+????10.0 ????10.0 ????10.0 ????10.O ??18.7 ??11.6 ??8.2 ??8.0 ??22.0 ??23.3 ??15.8 ??15.4 ????44 ????39 ????36 ????41 ????58 ????52 ????53 ????47
Embodiment 4
" canadian standard freeness testing apparatus " used in the evaluation of the dehydrating effect of this experimental series, is the conventional process of measuring the leaching feature according to SCAN-C21:65.All chemicals that add all carry out in " Britt Dynamic Drainage Jar (Britt power leaching jar) " that an outlet is jumped a queue, step mixing speed in 45 seconds process according to embodiment 1 is 1000 rpm, then the paper stock system is transferred in the beating degree instrument. the minimum hole at the bottom of the sealing beating degree testing apparatus, measure the time of 400 milliliters of batchings by screen filtration.Paper stock is taken from the enclosed grinding machine that uses waste water, denseness 0.14%, and electrical conductivity 8.0 ms/cm, pH is about 7.Table 4 is depicted as the dehydrating effect of the silica base particle of various dose, with SiO 2And based on dried paper stock system computing.
Table 4
Tested number Dose of polymer (kg/ton) ??SiO 2Dosage (kg/ton) Electrical conductivity (mS/cm) Dewatering time (second)
????P1 ????P2
????1 ????2 ????3 ????4 ????5 ????0.6 ????0.6 ????0.6 ????0.6 ????0.6 ????0 ????0.25 ????0.5 ????0.75 ????1 ????8.0 ????8.0 ????8.0 ????8.O ????8.0 ????100.4 ????66.4 ????58.3 ????50.0 ????44.6 ????103.2 ????92.5 ????85.8 ????76.0 ????79.2
Embodiment 5
Dehydrating effect is by embodiment 3 described evaluations in this experimental series, but uses sodium acetate (550 ppm Na +) and calcium chloride (1300 ppm Ca 2+) the two regulates electrical conductivity.
Be used for this experimental series like polymer among the embodiment 1 and the anionic inorganic particulate species.
Table 5 is depicted as the dehydrating effect of the silica base particle of various dose, with SiO 2And based on dried paper stock system computing.
Table 5
Tested number Dose of polymer (kg/ton) ??SiO 2Dosage (kg/ton) Electrical conductivity (mS/cm) Dewatering time (second)
????P1 ????P2
????1 ????2 ????3 ????4 ????5 ????6 ????2 ????1 ????2 ????3 ????2 ????2 ????1 ????3 ????3 ????3 ????1 ????2 ????2.5 ????10.0 ????10.0 ????10.0 ????10.0 ????10.0 ????16.1 ????10.7 ????6.8 ????5.3 ????9.7 ????7.9 ????18.2 ????14.7 ????13.5 ????14.0 ????20.4 ????14.8
Embodiment 6
In this experimental series dehydration and stay effect by embodiment 3 evaluation, use sodium acetate (550ppm Na +) and calcium chloride (1300ppm Ca 2+) combine and regulate electrical conductivity.
Be used for this experimental series like the polymer class among the embodiment 1.Used anionic microparticles material is the aqueous suspension system of powdery bentonite-Na in water.Bentonitic surface charge is about 0.33meq/g, and swelliong power is 41 milliliters (2 grams).The addition of bentonite clay particle is 8.0 kg/ton, with dried bentonite for the paper stock system computing.
Table 6 be depicted as the P1 of various dose and P2 dehydration and stay effect, with dry polymeric to dried paper stock system computing.
Table 6
Tested number Dose of polymer (kg/ton) Bentonite dosage (kg/ton) Electrical conductivity (mS/cm) Dewatering time (second) Turbidity (NTU)
P1 P2 P1 P2
1 2 3 4 1 2 3 4 8 8 8 8 10.0 10.0 10.0 10.0 13.6 10.8 8.48 7.42 18.5 20.6 24.8 26.6 41 29 20 18 47 41 36 36
Embodiment 7
Dehydrating effect is by embodiment 6 described evaluations in this experimental series, but uses sodium chloride to regulate electrical conductivity.
Polymer and the bentonite of embodiment 6 are used for these tests similarly.The addition of bentonite clay particle is 8.0 kg/ton, with dried bentonite to dried paper stock system computing.Table 7 be depicted as the P1 of various dose and P2 dehydration and stay effect, with dry polymeric to dried paper stock system computing.
Table 7
Tested number Dose of polymer (kg/ton) Bentonite dosage (kg/ton) Electrical conductivity (mS/cm) Dewatering time (second)
????P1 ????P2
????1 ????2 ????3 ????4 ????2 ????3 ????4 ????5 ????8 ????8 ????8 ????8 ??550ppm?Na +????2.5 ????2.5 ????2.5 ????2.5 ????15.3 ????11.9 ????8.6 ????6.8 ????17.5 ????14.1 ????9.8 ????8.2
????5 ????6 ????7 ????8 ????2 ????3 ????4 ????5 ????8 ????8 ????8 ????8 ?3320ppm?Na +????10.0 ????10.O ????10.0 ????10.O ????12.7 ????9.4 ????6.9 ????5.6 ????15.5 ????12.5 ????10.9 ????10.0
Embodiment 8
In this experimental series, dehydrating effect is by embodiment 3 described evaluations, but the use zinc chloride is regulated electrical conductivity.Polymer and the anionic inorganic microparticles of embodiment 1 are used for these tests similarly.Table 8 is depicted as the dehydration test result of the silica base particle of various dose, with SiO 2And based on dried paper stock system computing.
Table 8
Tested number Dose of polymer (kg/ton) ??SiO 2Dosage (kg/ton) Electrical conductivity (mS/cm) Dewatering time (second)
????P1 ????P2
????1 ????2 ????3 ????4 ????5 ????2 ????2 ????2 ????2 ????2 ????0 ????1 ????2 ????0 ????2 ??700ppm?Zn 2+????2.4 ????2.4 ????2.4 ??1400ppm?Zn 2+????4.5 ????4.5 ????13.6 ????7.9 ????5.5 ????18.0 ????6.3 ??22.7 ??8.5 ??5.6 ??28.0 ??11.4

Claims (17)

1. the suspension system of a filler that uses from cellulose fiber and the selectivity method of producing paper, this method is included in and adds filter aid and the retention agent that comprises cationic organic polymer in the suspension system; Suspension system moulding on the net and dehydration is characterized in that the electrical conductivity that cationic organic polymer has an aromatic radical and took off the suspension system of water on the net is at least 2.0mS/cm.
2. the suspension system of a filler that uses from cellulose fiber and the selectivity method of producing paper, this method is included in and adds filter aid and the retention agent that comprises cationic organic polymer in the suspension system; Suspension system moulding on the net and dehydration are to obtain wet web and plain boiled water, it is characterized in that cationic organic polymer has an aromatic radical, and the method further comprises the recirculation of plain boiled water and optionally adds the suspension system of fresh water with the desire dehydration of the filler of formation cellulose fiber and selectivity use that the fresh water amount of adding is less than the 30 tons/dried paper of producing per ton.
3. the described method of claim 1, it is characterized in that this method further comprises dewaters suspension system to obtain wet web and plain boiled water on the net, plain boiled water recirculation is also optionally added the suspension system of fresh water with the desire dehydration of the filler of formation cellulose fiber and selectivity use, and the fresh water amount of adding is less than the 20 tons/dried paper of producing per ton.
4. the described method of claim 1,2 or 3, the electrical conductivity that it is characterized in that taking off the suspension system of water on the net is at least 5.0mS/cm.
5. claim 1,2,3 or 4 described methods is characterized in that the dried paper of producing per ton adds and are less than 10 tons fresh water.
6. claim 1,2,3,4 or 5 described methods is characterized in that cationic organic polymer is the vinyl addition polymer, and it comprises one or more monomers of polymerized form, and at least a monomer has an aromatic radical.
7. the described method of aforementioned each claim is characterized in that cationic organic polymer is a polymer based on acrylamide.
8. the described method of aforementioned each claim is characterized in that it is the cationic monomer of the polymerized form with an aromatic radical of representative that cationic organic polymer comprises with general formula (I):
Figure 9980554800031
R in the formula 1Be H or CH 3R 2And R 3It respectively is the alkyl of 1-3 carbon atom; A 1Be O or NH; B 1Be the alkylidene or the hydroxy propylidene of 2-4 carbon atom; Q is a benzyl; X -It is the phase pair anion.
9. the described method of aforementioned each claim is characterized in that the weight average molecular weight of cationic organic polymer is at least 1,000,000.
10. the described method of aforementioned each claim is characterized in that cationic organic polymer is from comprising that 5-20 mole % has the mixture preparation of other copolymerisable monomer of the cationic monomer of an aromatic radical and 95-80 mole %.
11. the described method of aforementioned each claim is characterized in that filter aid and retention agent further comprise the anionic inorganic particle.
12. the described method of aforementioned each claim is characterized in that the anionic inorganic particle is selected from silica base particle or bentonite.
13. claim 11 or 12 described methods is characterized in that the anionic inorganic particle is selected from the silica base particle of aluminium modification.
14. the described method of aforementioned each claim is characterized in that filter aid and retention agent further comprise a low molecular weight cationic organic granular.
15. the described method of aforementioned each claim is characterized in that filter aid and retention agent further comprise an aluminium compound.
16. the described method of aforementioned each claim is characterized in that the suspension system of dewatering contains divalence and the polyvalent cation of 200ppm at least on the net.
17. the described method of aforementioned each claim is characterized in that suspension system comprises regenerated fiber.
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