CN104271836A - Controllable filler prefloculation using a dual polymer system - Google Patents

Controllable filler prefloculation using a dual polymer system Download PDF

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Publication number
CN104271836A
CN104271836A CN201380019024.5A CN201380019024A CN104271836A CN 104271836 A CN104271836 A CN 104271836A CN 201380019024 A CN201380019024 A CN 201380019024A CN 104271836 A CN104271836 A CN 104271836A
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CN
China
Prior art keywords
flocculant
filler
dispersion
paper
flocculate
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Pending
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CN201380019024.5A
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Chinese (zh)
Inventor
陈卫国
R·T·格雷
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ChampionX LLC
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Ondeo Nalco Co
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Priority claimed from US13/449,888 external-priority patent/US8747617B2/en
Application filed by Ondeo Nalco Co filed Critical Ondeo Nalco Co
Publication of CN104271836A publication Critical patent/CN104271836A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • D21H17/675—Oxides, hydroxides or carbonates
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • 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
    • 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
    • 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
    • D21H21/14—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 characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

A method of preparing a stable dispersion of flocculated filler particles for use in papermaking processes comprises sequential addition of a first flocculating agent to an aqueous dispersion of filler particles followed by shearing of the dispersion, followed by addition of a second flocculating agent to the dispersion and further shearing of the resultant filler flocs to the desired particle size resulting in shear resistant filler flocs with a defined and controllable size distribution. In addition, a neutralizing coagulant can be added to the dispersion to partially or completely neutralize the charge of the filler before the first flocculating agent is added.

Description

The controllable packing of Dual polymerization objects system is used to flocculate in advance
The cross reference of related application
The application is the part continuation application of the unsettled U.S. Patent Application Serial Number 11/854,044 in submission on September 12nd, 2007.
About the research of federal funding or the statement of exploitation
Inapplicable.
Background of invention
The present invention relates to the pre-flocculation of the filler for papermaking, especially, disclose that there is restriction under high filler solid with preparation that the is anti-shearing filler flocculate of controlled particle size distribution.
The filer content improved in printing and writing paper causes great interest, owing to improving product quality and reducing raw material and energy ezpenditure.But, with filler as calcium carbonate and clay substituted cellulose fiber reduce the intensity of finished product paper.Another problem when improving filer content is the difficulty keeping filler equally distributed increase in three dimensional paper structure.The means reducing these negative influences increasing filer content lead at green end filler being joined paper machine to flocculate in advance to filler before system.
The definition of term " pre-flocculation " is by filler particles being modified as agglomerate with coagulating agent and/or flocculating agent process before filler particles is added in paper stock.The flocculation treatment of technique and shearing force determine the size distribution and the stability that join flocculate before in paper stock.The chemical environment existed in modern high speed papermaking and high fluid shear rate need filler flocculate to be stable and shear-stable.The paper strength that the flocculate size distribution that pre-flocculation treatment provides should be minimized under the filer content of increase reduces, and minimizes the loss of the light efficiency rate from filler particles, and minimizes the negative effect to the paper uniformity and impressionability.In addition, whole system must be economically feasible.
Therefore, the combination of high shear stability and sharp domain size distribution is that the pre-flocculation technique of filler is successfully crucial.But the filler flocculate only formed by the low molecular weight coagulating agent comprising the conventional starch used tends to have relatively little particle diameter broken under the high shear force of paper machine.The filler flocculate that single high molecular flocculating agent is formed tends to have the distribution of unmanageable wide particle diameter, and this domain size distribution becomes poorer under higher filler solid level, mainly because the coagulant solution of viscosity is to the bad mixing of slurry.So, there is lasting demand for the pre-flocculation technique improved.
Unless pointed out so particularly, it is admitting about " prior art " of the present invention that the technology described in this section is not intended to form to any patent mentioned, open or out of Memory here.In addition, this section should not be construed as other relevant information showing to have carried out retrieving or do not have definition in 37C.F.R. § 1.56 (a).
Brief summary of the invention
At least one embodiment relates to the method with the stabilising dispersions of the flocculation filler particles of specified particle diameter distribution for the preparation of paper technology, and described method comprises: water-borne dispersions a) providing filler particles; The amount that b) described filler particles can not be caused significantly to flocculate to be enough to Homogeneous phase mixing in described dispersion adds the first flocculant in described dispersion; C) under described first flocculant exists, in described dispersion, the second flocculant is added with the amount being enough to the flocculation causing described filler particles; And d) optionally shear the dispersion of flocculating to provide the dispersion of the filler flocculate with required particle diameter.
At least one embodiment relates to the method by pulp manufacture paper products, comprise: form aqueous fiber element paper making stock furnish, the water-borne dispersions of the filler flocculate of preparation as described herein is added in described batching, by described batching draining to form sheet material, and this sheet material dry.Form described paper making stock furnish, the step of draining and drying can carry out with any usual manner known in those skilled in the art.
At least one embodiment relates to the paper products of the filler flocculate introducing preparation as described herein.
Accompanying drawing is sketched
Hereafter specifically describe detailed description of the present invention with reference to the accompanying drawings, wherein:
Fig. 1 illustrates the MCL temporal resolution of flocculation reaction.
Detailed Description Of The Invention
There is provided definition below to determine with term in this application and particularly claim how decipher.Tissue definition is only conveniently, instead of intends any definition of restriction to any specific classification.For the object of the application, these terms are defined as follows:
" coagulating agent " refers to the composition had than flocculating agent more high charge density and more low-molecular-weight material, and when in the liquid being joined the suspended particulate containing fine separation, the mechanism that can be neutralized by ionic charge is made these solids unstable and assembles.
" flocculating agent (Flocculant) " refers to have low charge density and high molecular (more than 1,000,000) composition of material, when in the liquid being joined the suspended particulate containing fine separation, can these solids be made unstable by the mechanism of bridge joint between particle and assemble.
" flocculant (Flocculating Agent) " refers to and to make the unstable with the fine suspended particulate be separated of the colloid in this liquid when joining in liquid and the composition of the material assembled, and flocculating agent and coagulating agent can be flocculants.
" GCC " refers to the calcium carbonate ground, and it is obtained by the calcium carbonate rock grinding natural generation.
" PCC " refers to the winnofil of synthesis preparation.
The implication pointed out in Reference source that is in above-mentioned definition or the description pointed out in other place of the application and normally used, dictionary or that be incorporated in the application by reference (clear and definite or imply) is inconsistent, the term of the application and claim is interpreted as especially to be explained according to the definition in the application or describe, instead of explains according to common definition, dictionary definition or the definition that is incorporated to by reference.Based on as mentioned above, only having at term to make an explanation just in understandable situation to it by dictionary, if term is by Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John & Sons, Inc.) define, then this definition will control described term and how to define in the claims.
Filler useful be in the present invention know and commercially available.They can comprise usually for improving Paper or cardboard sheet opacity or brightness, increase smoothness or any inorganic or organic granular reduced costs or pigment.Representative filler comprises calcium carbonate, kaolinton, talcum, titanium dioxide, hibbsite, barium sulfate, magnesium hydroxide etc.Calcium carbonate comprises GCC, chalk, the PCC of any form and the PCC of dispersed slurry form of the slurry form of drying or dispersion.Some examples of GCC and PCC slurry, in the U.S. Patent Application Serial Number 12/323 of CO-PENDING, provide in 976.GCC or PCC of dispersed slurry form is usually with acrylic acid polymer dispersant or the preparation of polyphosphate sodium dispersant.Give calcium carbonate granule significant anionic charge for often kind in these dispersants.Kaolinton slurry also can disperse with acrylic acid polymer or polyphosphate sodium.
In one embodiment, filler is selected from calcium carbonate and kaolinton and combination thereof.
In one embodiment, filler be selected from precipitation calcium carbonate, the calcium carbonate and kaolinton and composition thereof that grind.
When using together with being with the filler of cationic charge, the first flocculant is preferably cationic polymer flocculating agent; When using together with being with the filler of anionic charge, the first flocculant is preferably anionic polymer flocculating agent.But as long as it can not cause remarkable flocculation in Homogeneous phase mixing to high solid slurry, then it can be anion, nonionic, amphion (zwitterionic) or both sexes (amphoteric).
The definition " not causing remarkable flocculation " is the flocculation not having above-mentioned filler under the first flocculant exists, or forms those flocculates and flocculate unstable under gentle shearing condition of being less than and producing when adding the second flocculant.Gentle shearing is defined as in 600ml beaker with the shearing that IKA RE 16 stirring motor provides with 800rpm 5cm diameter quaterfoil turbine wheel mixing 300ml sample.This shearing should to modern paper machine to lead the shearing existed in system similar.
Suitable flocculating agent generally has more than 1, the molecular weight of 000,000, and often exceeds 5,000,000.
Polymer agglomerates agent is usually by one or more CATION, the vinyl addition polymerization reaction of anion or non-ionic monomer, the copolymerization of one or more cationic monomers and one or more non-ionic monomers, the copolymerization of one or more anionic monomers and one or more non-ionic monomers, the copolymerization of one or more cationic monomers and one or more anionic monomers and one or more optional non-ionic monomers is to produce both sexes (amphoteric) polymer, or one or more zwitterionic monomers and one or more optional non-ionic monomers polymerization to form amphoteric ion polymer to prepare.One or more zwitterionic monomers and one or more optional non-ionic monomers also can with one or more anion or cationic monomer copolymerization, to give this amphoteric ion polymer CATION or anionic charge.Suitable flocculating agent generally has the charge content being less than 80mol%, is often less than 40mol%.
Although cationic polymer flocculating agent can use cationic monomer to be formed, some nonionic ethylene based addition polymer also can be made to react and the polymer of generating strap cationic charge.Such polymer comprises those polymer being produced Mannich (Mannich) derivative by polyacrylamide and dimethylamine and formaldehyde reaction and prepared.
Similarly, although anionic polymer flocculating agent can be formed with anionic monomer, also can some nonionic ethylene based addition polymer of modification with formed band anionic charge polymer.The polymer of this type comprises such as by those polymer prepared by hydrolysis of polyacrylamide.
Flocculating agent can in solid form, as aqueous solution, as water-in-oil emulsion or as the dispersion in water.Representational cationic polymer comprises copolymer and the trimer of (methyl) acrylamide and dimethylaminoethyl methacrylate (DMAEM), dimethylaminoethyl acrylate (DMAEA), acrylic acid lignocaine ethyl ester (DEAEA), diethylaminoethyl methacrylate (DEAEM) or their quaternary ammonium form, prepared by described quaternary ammonium form dimethyl suflfate, chloromethanes or chlorotoluene.Representational anionic polymer comprises the copolymer of acrylamide and sodium acrylate and/or 2-acrylamide-2-methylpro panesulfonic acid (AMPS) or has been hydrolyzed that some acrylamide group is converted into acrylic acid methacrylamide homopolymer.
In one embodiment, flocculating agent has the RSV of at least 3dl/g.
In one embodiment, flocculating agent has the RSV of at least 10dl/g.
In one embodiment, flocculating agent has the RSV of at least 15dl/g.
" RSV " used herein represents reduced viscosity (reduced specific viscosity).According to " the Determination of Molecular Weights " of Paul J.Flory in publishing house of Cornell University " Principles of Polymer Chemistry " (1953) the VII chapter 266-316 pages of New York Ithaca, be essentially in polymer homolog that is linear and solvation well a series of, " reduced viscosity (the RSV) " measured value for the polymer solution of dilution is the display of polymer chain length peace average molecular weight.Under given polymer concentration and temperature, measure RSV, and calculate as follows:
RSV=[(η/η o)-1]/c, the wherein viscosity of η=polymer solution, η othe viscosity of=solvent at the same temperature, the concentration of polymer in c=solution.
The unit of concentration " c " is (gram/100ml or g/ decilitre).Therefore, the unit of RSV is dL/g.Except as otherwise noted, use 1.0 molar nitric acid sodium solutions to measure RSV.Polymer concentration in this solvent is 0.045g/dL.RSV measures at 30 DEG C.Viscosities il and η is measured with Size75Cannon Ubbelohde semimicro dilution viscometer 0.This viscosimeter is arranged on position completely vertical in the constant temperature bath being adjusted to 30 ± 0.02 DEG C.Intrinsic typical error in the RSV calculating of polymer described herein is about 0.2dL/g.When two polymer homologs in a series have similar RSV ' s, show that they have similar molecular weight.
As mentioned above, to be enough to Homogeneous phase mixing and the amount that filler particles significantly flocculates can not be made to add the first flocculant in dispersions.In one embodiment, the dosage of the first flocculant is between 0.2 pound/ton-6.0 pounds/tons treated fillers.In one embodiment, the dosage of flocculating agent is between 0.4 pound/ton-3.0 pounds/tons treated fillers.For object of the present invention, " pound/ton " is the dosage unit of the poundage of the living polymer (coagulating agent or flocculating agent) representing every 2000 pounds of fillers.
Second flocculant can be any material that can cause filler flocculation under the first flocculant exists.In one embodiment, the second flocculant is selected from particulate, coagulating agent, flocculating agent and composition thereof.
The particulate be applicable to comprises siliceous material and polymer particles.Representational siliceous material comprises silica-based particles, silica mlcrogels, cataloid, Ludox, Silica hydrogel, polysilicate, cationic silicon dioxide, aluminosilicate, polysialates, borosilicate, poly-borosilicate, zeolite, and the expansive clay of synthesis or natural generation.Expansive clay can be bentonite, hectorite, terre verte, imvite, nontronite, talcum powder, sauconite, mormite, attapulgite and sepiolite.
Polymer particles useful in the present invention comprises anion, CATION or both sexes organic fine particles.These particulates have the solubility in limited water usually, and it can be crosslinked, and have the non-unswollen particle diameter being less than 750nm.
Anionic organic particles comprises US 6,524, describe in 439 those, and those particulates prepared by hydrolyzed acrylamide polymer particles or prepared by polymeric anion monomer such as (methyl) acrylic acid and salt thereof, 2-acrylamide-2-methylpro panesulfonic acid ester, sulfoethyl-(methyl) acrylate, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or other binary acid or its salt or their mixture.These anionic monomers also can with non-ionic monomer such as (methyl) acrylamide, N-alkyl acrylamide, N, N-dialkylacrylamides, (methyl) methyl acrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methyl formamide, vinyl acetate, NVP and their mixture copolymerization.
Cationic organic particles comprises US 6,524, those described in 439, with by making as (methyl) acrylate of diallyldialkylammonium halide, acryloxyalkyl trimethyl ammonium chloride, dialkylaminoalkyl compounds and their salt and quaternary ammonium salt (quaternaries), and N, the acid of N-dialkylaminoalkyl (methyl) acrylamide, (methyl) acrylamidopropyl trimethyl ammonium chloride and N, N-dimethyl amino ethyl acrylate etc. or the monomer polymerization of quaternary ammonium salt and prepare those.These cationic monomers also can with non-ionic monomer such as (methyl) acrylamide, N-alkyl acrylamide, N, N-dialkylacrylamides, (methyl) methyl acrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methyl formamide, vinyl acetate, NVP and their mixture copolymerization.
Both sexes organic fine particles is prepared by the combination being polymerized at least one at least one in above-mentioned anionic monomer, at least one in above-mentioned cationic monomer and optional above-mentioned non-ionic monomer.
In organic fine particles, the polymerization of above-mentioned monomer completes usually under the existence of polyfunctional crosslinking agent.These crosslinking agents are described in US 6, and 524, in 439, there are at least two double bonds, a double bond and a reactive group or two reactive groups.The example of these reagent be N, N-di-2-ethylhexylphosphine oxide (methyl) acrylamide, polyethylene glycol two (methyl) acrylate, N-vinyl acrylamide, divinylbenzene, triallyl ammonium, N-methylallylacrylamide glycidyl (methyl) acrylate, acrolein, n-methylolacrylamide, dialdehyde as glyoxal, di-epoxy compounds and chloropropylene oxide.
In one embodiment, the dosage of particulate is between 0.5 pound/ton-8 pounds/tons treated fillers.In one embodiment, the dosage of particulate is between 1.0 pounds/ton-4.0 pounds/tons treated fillers.
Suitable coagulating agent generally has the molecular weight lower than flocculating agent, and has high cationic charge groups density.Coagulating agent useful be in the present invention know and commercially available.They can be inorganic or organic.Representational inorganic coagulant comprises alum, sodium aluminate, polyaluminium chloride or PAC (it can also be called aluminium chlorohydrate, hydroxide aluminium chloride and poly-polymeric aluminum chloride), Sulfated polyaluminium chloride, polymeric aluminum sulfate silicate (polyaluminum silica sulfate), ferric sulfate, iron chloride etc. and their blend.
Many organic coagulants are formed by polycondensation.The example of such polymer comprises epichlorohydrin-dimethylamine (EPI-DMA) copolymer and the EPI-DMA copolymer crosslinked with ammonia.
Extra coagulating agent comprises the polymer of ethylene dichloride and ammonia or adds or do not add the ethylene dichloride of ammonia and the polymer of dimethylamine; The condensation polymer of polyfunctional amine and ethylene dichloride or polyfunctional acid, described polyfunctional amine is diethylenetriamines, tetren, hexamethylene diamine etc. such as, described polyfunctional acid such as ethanedioic acid; With the polymer prepared by condensation reaction, such as melamino-formaldehyde resin.
Extra coagulating agent comprises the vinyl-addition polymer of band cationic charge, such as (methyl) acrylamide, diallyl-N, the dibasic ammonium halide of N-, dimethylaminoethyl methacrylate and its quaternary ammonium salt, dimethylaminoethyl acrylate and its quaternary ammonium salt, methacryiamidopropyl trimethyl ammonium chloride, diallyl methyl (β-propionamido-) ammonium chloride, (Beta-methyl acrylyl oxy-ethyl) trimethylammoniumethyl sulfate, quaternised polyvinyl base lactam (quaternized polyvinyllactam), vinylamine and reacted to produce the acrylamide in Mannich or season Mannich derivative (quaternary Mannich derivative) or the polymer of Methacrylamide, copolymer and trimer.Suitable quaternary ammonium salt can use chloromethanes, dimethyl suflfate or chlorotoluene to prepare.Trimer can comprise anionic monomer, such as acrylic acid or 2-acrylamide-2-methylpro panesulfonic acid, as long as the overall charge on this polymer is cationic.No matter be Addition on ethylene or condensation, the molecular weight ranges of these polymer is paramount to millions of from being low to moderate hundreds of.
The polymer of cationic, anion or the both sexes that its chemical property is described as flocculating agent is above comprised as other polymer that the second flocculant is useful.Difference between these polymer and flocculating agents is mainly molecular weight.
Second flocculant can be used alone, or the second flocculant conbined usage extra with one or more.In one embodiment, after adding the second flocculant, in the filler slurry of flocculation, add one or more particulates.
With the amount being enough to cause the flocculation of filler particles under the first flocculant exists, the second flocculant is joined in described dispersion.In one embodiment, the dosage of the second flocculant is between 0.2 pound/ton-8.0 pounds/tons treated fillers.In one embodiment, the dosage of second component is between 0.5 pound/ton-6.0 pounds/tons treated fillers.
In one embodiment, in the dispersion can flocculated at the forward direction of shearing, add one or more particulates, to provide extra flocculation and/or narrow size distribution.
In one embodiment, the second flocculant and the first flocculant are that electric charge is contrary.
In one embodiment, the first flocculant is cationic and the second flocculant is anion.
In one embodiment, the first flocculant is selected from copolymer and its mixture of acrylamide and dimethylaminoethyl methacrylate (DMAEM) or dimethylaminoethyl acrylate (DMAEA).
In one embodiment, the first flocculant is the copolymer of acrylamide and dimethylaminoethyl acrylate (DMAEA), and its cationic charge content is 5-50 % by mole and RSV > 15dL/g.
In one embodiment, the second flocculant is selected from the acrylamide of partial hydrolysis and the copolymer of acrylamide and sodium acrylate.
In one embodiment, the second flocculant is the acrylamide-sodium acrylate copolymer of the RSV with 5-40mol% anionic charge and 0.3-5dL/g.
In one embodiment, the first flocculant is anion and the second flocculant is cationic.
In one embodiment, the first flocculant is selected from the acrylamide of partial hydrolysis and acrylamide and sodium acrylate copolymer.
In one embodiment, the first flocculant is the copolymer of acrylamide and sodium acrylate, and it has the anionic charge of 5-75 % by mole and the RSV of at least 15dL/g.
In one embodiment, the second flocculant is selected from epichlorohydrin-dimethylamine (EPI-DMA) copolymer, the EPI-DMA copolymer crosslinked with ammonia and the dibasic ammonium chloride homopolymer of diallyl-N, N-.
In one embodiment, the second flocculant is the diallyldimethylammonium chloride homopolymers of the RSV with 0.1-2dL/g.
In one embodiment, the second flocculant is selected from copolymer and its mixture of acrylamide and dimethylaminoethyl methacrylate (DMAEM) or dimethylaminoethyl acrylate (DMAEA).
In one embodiment, the second flocculant is the copolymer of acrylamide and dimethylaminoethyl acrylate (DMAEA), and its cationic charge content is 5-50 % by mole and RSV > 15dL/g.
Dispersion according to filler flocculate of the present invention was prepared before adding paper making stock furnish.This can be undertaken by batch mode or continuous mode.Packing density in these slurries is less than 80 quality % usually.More generally between 5 quality %-65 quality %.
Batch process can be made up of the large mixing channel of the rotary propeller type blender with top set.Filler slurry is filled with in this mixing channel, with continuous stirring the first flocculant of aequum is fed in this slurry.This slurry and flocculating agent mixing are enough to make the first flocculant equally distributed time in whole system, usually mixing about 10 to 60 seconds, this depends on the mixed tensor of use.Then add the second flocculant of aequum while carrying out stirring with the mixing velocity being enough to broken filler flocculate under the incorporation time increased, the incorporation time of described increase usually at several seconds to a few minutes, this depends on the mixed tensor of use.Alternatively, particulate adds to cause flocculation again and the size distribution of constriction flocculate as three components.When obtaining suitable filler flocculate size distribution, mixing velocity is reduced to the level that this flocculate is stable.Then this collection of flocculation filler is transferred to larger mixing channel, it has is enough to keep the mixing in dispersions of filler flocculate even suspension.The filler of flocculation is pumped into paper making stock furnish from this mixing channel.
In a continuous process, the first flocculant of aequum is pumped into and comprises in the pipeline of filler, and mix with online static mixer when needing.The length being enough to allow filler and the well-mixed pipe of flocculating agent or mixer can be comprised before the second flocculant of injection appropriate amount.Then the second flocculant is pumped into and comprise in the pipe of this filler, and mix with online static mixer when needing.Alternatively, particulate adds to cause flocculation again and the size distribution of constriction flocculate as three components.Then need mixed at high speed to obtain required filler flocculate size distribution.Regulate the shear rate of mixing arrangement or incorporation time can control flocculate size distribution.Continuous processing makes it can use adjustable shear rate in the device of fixed volume.At United States Patent (USP) 4,799, describe a kind of such device in 964.This device is a kind of adjustable speed centrifugal pump, and when it runs under the back-pressure exceeding its cut-out pressure, it is as the mechanical shearing device work not with pumpability.Other suitable shear comprises the high intensity mixer of nozzle, Scroll-type emulsifier unit or the adjustable speed in fixed volume container with adjustable pressure drop.After the shearing, the filler slurry of flocculation is fed directly in paper making stock furnish.
In batch process as above and continuous processing, filter or sieve can be used to remove oversize filler flocculate.Which eliminate the potential mechanical performability and paper quality problems that cause owing to comprising large filler flocculate in Paper or cardboard.
In one embodiment, the median particle diameter of filler flocculate is at least 10 μm.In one embodiment, the median particle diameter of filler flocculate is between 10 μm and 100 μm.In one embodiment, the median particle diameter of filler flocculate is between 10 μm and 70 μm.
In at least one embodiment, use U.S. Patent application 12/975, in 596 describe composition and/or method at least one put into practice the present invention.In at least one embodiment, use United States Patent (USP) 8,088, in 213 describe composition and/or method at least one put into practice the present invention.
Embodiment
Can understand foregoing teachings better with reference to the following examples, the described embodiment of proposition is the object illustrated, instead of intends to limit the scope of the invention:
embodiment 1-7
Filler for each embodiment is the scalenohedron PCC (can be used as Albacar HO to obtain from Specialty Minerals Inc., Bethlehem, PA USA) not disperseing or disperse.When using the PCC do not disperseed, with running water, dryed product is diluted to 10% solid.When using the PCC of dispersion, its slurry as 40% solid obtains, and is diluted to 10% solid with running water.In flocculation process, use Lasentec, Redmond, WA to produce s400FBRM (Focused Beam Reflectance measurement) probe is with the size distribution of three seconds interval measurement PCC.FBRM operation theoretical description behind can be found in United States Patent (USP) 4,871,251.The mean chord (MCL) of PCC flocculate is measured as the entirety of flocculating degree.Laser microprobe is inserted in the 600mL beaker of the 10%PCC slurry containing 300mL.This solution was stirred at least 30 seconds with IKA RE 16 stirring motor with 800rpm before adding flocculant.
The first flocculant is slowly added with syringe in the process of 30 seconds to 60 seconds.When use the second flocculant, wait ten seconds with after making the first flocculant mixing, add the second flocculant in the mode similar to the first flocculant.Finally, when adding particulate, wait ten seconds with after making the second flocculant mixing, add particulate in the mode similar to flocculant.Before the use, flocculating agent is diluted to based on solid 0.3% concentration, coagulating agent is diluted to based on solid 0.7% concentration, starch is diluted to based on solid 5% concentration, particulate is diluted to based on solid 0.5% concentration.Typical MCL time resolution rate curve is shown in Figure 1.
The MCL time resolution rate curve of Fig. 1 is used s400FBRM record.At point 1 place, the first flocculant is introduced in slurry, and under 800rpm mixing velocity, MCL raises, and then declines fast, shows that filler flocculate is unstable under this shearing.At point 2 place, introduce the second flocculant, and MCL also raises and then slightly declines under 800rpm mixing.At point 3 place, introduce particulate, MCL raises rapidly and then reaches plateau, shows that filler flocculate is stable under 800rpm mixing.Be elevated to 1500rpm once shear, MCL just starts to decline.
For each filler flocculating experiment, have recorded the maximum MCL after flocculant adds, be listed in Table II.Maximum MCL indicates the degree of flocculation.Then slurry is stirred 8 minutes at 1500 rpm, to test filler flocculate stability under high shear conditions..Be recorded in the MCL value of 4 minutes and 8 minutes, and list in respectively in Table III and IV.
Also characterized the domain size distribution of filler flocculate by laser light scattering with the Mastersizer Micro available from Malvern Instruments Ltd., Southborough, MA USA.This analysis polydispersion model and image 4PAD (presentation 4PAD) carry out.This image assumes that the refractive index of filler is 1.60, and is 1.33 as the refractive index of the water of continuous phase.The distributed mass intermediate value floc size D (V, 0.5) of volume weighting (volume-weighted), the span of distribution and the uniformity of distribution represent.Span and uniformity are defined as:
Herein, D (v, 0.1), D (v, 0.5) and D (v, 0.9) are defined as the diameter of 10vol%, 50vol% and the 90vol% being equal to or greater than filler particles respectively.V iand D ivolume fraction and the diameter of the particle in set of dimensions i.Less span and uniformity value represent more uniform domain size distribution, and this it has been generally acknowledged that to have good performance in papermaking.In each embodiment under maximum MCL, 1500rpm shear 4 minutes and 8 minutes time these features of filler flocculate list in Table II, III and IV.List in Table I for PCC type, flocculant and flocculant dose in each embodiment.
embodiment 8
This description of test uses the feasibility of continuous processing flocculation PCC slurry.Do not disperse PCC (as Albacar HO available from Specialty Minerals Inc., Bethlehem, PA USA) pump in the bucket of five gallon bottle 10% solid in the running water of a collection of 18 liters with centrifugal pump using 7.6L/min.The flocculating agent solution A of 0.3% solid of 1.0 pounds of/ton of active agent dose is fed in this PCC slurry at centrifugal pump entrance with progressive cavity pump (progressive cavity pump).Then by the solution feed of 0.7% solid of the coagulating agent A of PCC and 1.0 pound of/ton of active agent dose in static mixer.Measure the size distribution of this filler flocculate with Mastersizer Micro, and be reported in Table II.In the mode identical with embodiment 1-7, in beaker, stir the slurry that obtains of 300mL 8 minutes with 1500rpm.The feature of the filler flocculate when 4 minutes and 8 minutes is listed in Table III and IV respectively.
embodiment 9
Filler slurry is identical with embodiment 8 with experiment flow, and just coagulating agent A is fed in centrifugal pump, and flocculating agent A is fed in static mixer.The size characteristic of filler flocculate is listed in Table II, III and IV.
Table I. PCC type, the flocculant of embodiment 1 to 9 describe and flocculant dose
Table II. maximum MCL or 1500rpm shears the feature of the filler flocculate of lower 0 minute.
Embodiment MCL(μm) D(v,0.1)(μm) D(v,0.5)(μm) D(v,0.9)(μm) Span Uniformity
1 12.52 10.42 23.07 46.48 1.56 0.49
2 16.81 13.48 32.08 98.92 2.66 0.83
3 30.13 53.94 130.68 228.93 1.34 0.41
4 18.52 19.46 43.91 90.86 1.63 0.51
5 38.61 67.2 147.73 240.04 1.17 0.36
6 34.39 53.21 111.48 209.04 1.40 0.43
7 45.63 34.17 125.68 240.63 1.64 0.52
8 NA 24.4 58.17 125.47 1.74 0.52
9 NA 29.62 132.79 234.62 1.54 0.46
Table III .1500rpm shears the filler flocculate feature after lower 4 minutes
Embodiment MCL(μm) D(v,0.1)(μm) D(v,0.5)(μm) D(v,0.9)(μm) Span Uniformity
1 7.46 4.76 9.51 17.39 1.33 0.41
2 13.21 11.29 27.26 91.78 2.95 0.92
3 16.13 13.25 42.73 142.37 3.02 0.92
4 13.86 14.91 28.46 51.63 1.29 0.4
5 17.66 21.8 58.08 143.31 2.09 0.65
6 14.77 15.77 35.62 85.29 1.95 0.6
7 21.26 12.88 45.00 197.46 4.10 1.24
8 NA 14.91 35.88 76.29 1.71 0.53
9 NA 8.08 48.64 152.89 2.98 0.93
Table IV .1500rpm shears the filler flocculate feature after lower 8 minutes
Embodiment MCL(μm) D(v,0.1)(μm) D(v,0.5)(μm) D(v,0.9)(μm) Span Uniformity
1 7.02 4.01 8.03 15 1.37 0.43
2 12.43 8.57 20.47 48.67 1.96 0.67
3 13.62 9.46 28.93 110.3 3.49 1.06
4 12.88 12.48 23.48 42.36 1.27 0.45
5 15.30 15.64 41.16 106.73 2.21 0.7
6 12.06 10.47 23.88 52.81 1.77 0.62
7 17.42 9.2 30.37 176 5.49 1.53
8 NA 12.67 30.84 65.95 1.73 0.53
9 NA 6.66 34.82 116.3 3.15 0.99
As shown in Table II-IV, only only used the filler flocculate formed in the embodiment 1 of cationic starch is shear instability.On the other hand, as shown in embodiment 2 to 9, the filler flocculate that multiple polymers is formed presents the shear stability of enhancing.Embodiment 2,4,6 and 8 shows filler flocculate prepared in accordance with the present invention, and embodiment 3,5,7 and 9 shows the filler flocculate prepared by existing method.Compared with the filler flocculate formed by existing method, generally there is after filler flocculate prepared in accordance with the present invention comes under shear narrower domain size distribution (as shown in the smaller value of span and uniformity in Table III and IV).
embodiment 10
The object of this embodiment is that the PCC flocculate of evaluation different size is on the impact of handmade paper physical property.The flow process described in this PCC sample embodiment 2 obtains, and the solids content except this PCC is 2%.There are by shearing different time preparation at 1500rpm four kinds of flocculations filler fioc sample (10-A, 10-B, 10-C and 10-D) in advance of different-grain diameter.Shear time and the grain diameter characteristic obtained are listed in Table V.
The thick stock of denseness 2.5% is prepared from the recycled fibers of the 80% hardwood dry pulp plate (hardwood dry lap pulp) and 20% that derive from American Fiber Resources (AFR) LLC, Fairmont, WV.Hardwood is refined the freedom into 300mL Canadian Standard Freeness (tappi test method T 227om-94) in Valley beater (available from Voith Sulzer, Appleton, WI).With running water, this thick stock is diluted to 0.5% denseness.
In dynamic drainage instrument, prepare handmade paper with the batching of 0.5% denseness of 800rpm mixing 650mL, the end sieve that the useful plastic solidification sheet of this dynamic drainage instrument band covers is to prevent drainage.Dynamic drainage instrument and blender can available from the Paper Chemistry Consulting Laboratory of New York Carmel, Inc..Start mixing, 1 gram of a kind of PCC sample is added after 15 seconds, then the GC7503 polyaluminium chloride solution adding 6 pounds/ton (based on products) at 30 seconds (can available from Gulbrandsen Technologies, Clinton, NJ, USA), it is that the sodium acrylate-acrylamide copolymer flocculating agent of 29mol% (can available from Nalco Company that the RSV adding 1 pound/ton (based on product) at 45 seconds is about 32dL/g and charge content, Naperville, IL USA), the borosilicate microparticle adding 3.5 pounds/ton (activating agents) at 60 seconds (can available from Nalco Company, Naperville, IL USA).
Stopped mixing at 75 seconds, batching is transferred in the deckle box of Noble & Wood handsheet mold.By 100 order forming net drainages, thus form the handmade paper of 8 " × 8 ".By two blotting paper and metallic plate to be put on wet handmade paper and by the roll-in of the metallic roll of 25 pounds six times, by handmade paper from paper mould net (sheet mold wire) pressing (couched).Remove forming net and a blotting paper, this handmade paper is put between two new blotting paper and press felt, and suppresses with 50psig with roll press.Remove all blotting paper, with being set as the drumdrier of 220 ℉ this handmade paper dry 60 seconds (end face is in the face of drying machine surface).The average basis weight of handmade paper is 84g/m 2.Handsheet mold, roll press and drumdrier can available from Adirondack Machine Company, Queensbury, NY.To the PCC sample of often kind of test, prepare five parts of handmade paper duplicate.
The handmade paper completed is store overnight under the TAPPI standard conditions of 50% relative humidity and 23 DEG C.To each paper, measure basic weight with tappi test method T 410om-98, measure content of ashes with tappi test method T 211om-93, measure brightness with ISO method of testing 2470:1999, measure opacity with ISO method of testing 2471:1998.With can available from Metso Automation, Helsinki, FI's formation analyzer measures formation of sheet (formation) (measuring of basis weight uniformity).What these were measured the results are shown in Table VI.The TENSILE STRENGTH of these paper is measured with tappi test method T 494om-01, measure Scott bond strength (Scott Bond) with tappi test method T 569pm-00, measure Z-to TENSILE STRENGTH (ZDT) with tappi test method T 541om-89.These the results are shown in Table VII.
Table V. the filler floc size feature of sample 10-A to 10-E.10-E sample is untreated PCC slurry.
Embodiment Shear time (s) MCL(μm) D(v,0.1)(μm) D(v,0.5)(μm) D(v,0.9)(μm) Span Uniformity
10-A 210 70.4 30.4 83.6 181.2 1.8 0.55
10-B 330 49.3 29.2 64.0 129.1 1.6 0.49
10-C 450 39.4 22.5 45.1 87.4 1.4 0.44
10-D 1500 29.8 13.8 25.8 46.3 1.3 0.39
10-E NA 9.24 0.64 1.54 3.28 1.7 0.66
Table VI. there is the optical property of the paper of different size filler flocculate.
Table VII. there is the mechanical intensive property of the paper of different size filler flocculate.
As shown in Table V, along with the increase of time under 1500rpm shears, the size of filler flocculate reduces, and passes through the feasibility of time controling filler floc size under high shear is described.By often kind of handmade paper prepared in four kinds of pre-flocculated fillers (10-A to 10-D) and untreated filler (10-E), there is rough equal content of ashes and basic weight, as shown in Table VI.Increase floc size and do not damage brightness, but slightly reduce evenness and the opacity of paper.The mechanical strength of paper, as by Z-to measured by TENSILE STRENGTH, Scott bond strength, tensile figure and tensile energy absorption (TEA), increase along with filler floc size and significantly increase.This is shown in Table VII.In general, higher intermediate value PCC floc size causes the paper strength raised.In practice, the slightly damaged PCC content that can increase paper by constant of opacity improves paper strength and is compensated.
In at least one embodiment, the method for the pre-flocculation filler particles of paper technology comprises: water-based slurry a) providing filler particles; B) under the condition of highly mixing, in this dispersion, the first flocculant is added; D) under highly mixing, the second flocculant is added with the amount being enough to cause the flocculation of this filler particles under the first flocculant exists; And e) optionally, shear the dispersion of this flocculation, to provide the dispersion of the filler flocculate with required particle diameter.Preferably, the first flocculant is the one in above described anionic coagulation agent.Preferably, the second flocculant is the one above in described cationic flocculants.These two kinds of flocculating agents can have high molecular and low charge density extremely middle charge density separately.
Not wish by theoretical or design limit, it is believed that the first high molecular weight flocculants was formed before absorption and run through the equally distributed mixture of above-mentioned slurry.This equally distributed mixture is assisted CATION second flocculant effectively quality to be moved to and is formed floc particles together.As illustrated in the following embodiments, the new opplication of the two kinds of high molecular weight flocculants being used for controlling domain size distribution in slurry of this embodiment creates beyond thought effective flocculate and produces.Reference example 11-16 can understand this embodiment best.
embodiment 11-12
With running water, scalenohedron PCC (can available from Omya as Syncarb S NY) is diluted to 10% solid.Use with three seconds intervals during flocculating s400FBRM measures the size distribution of filler.Laser microprobe is inserted in the 600mL beaker of the 10%PCC slurry containing 300mL.Before adding flocculant, stir this solution at least 30 seconds with IKA RE 16 stirring motor with 800rpm.
First flocculant is slowly added in the process of a few minutes as dilute solution syringe.When use the second flocculant, wait for ten seconds with make first flocculant mixing after, add the second flocculant in the mode similar to the first flocculant.Then this slurry is stirred 2 to 4 minutes at 1500rpm, to test filler flocculate stability under high shear conditions..The PCC type, flocculant and the flocculant dose that use in these embodiments are listed in Table VIII, and the sign of these particles obtained is listed in Table I X.
embodiment 13-16
This description of test uses the feasibility of continuous processing flocculation PCC slurry.Do not disperse PCC (can available from Specialty Minerals Inc., Bethlehem, PA USA as Albacar HO) pump in the bucket of five gallon bottle 10% solid in the running water of a collection of 18 liters with centrifugal pump using 7.2kgPCC/min.First flocculant solution of suitable dosage is fed in this PCC slurry at centrifugal pump entrance with progressive cavity pump.Then PCC is fed in static mixer together with the second flocculant of suitable dosage.Measure the size distribution of filler flocculate with Mastersizer Micro, and be reported in Table X.By this sample that circulates through centrifugal pump, the sample obtained is exposed to extra shearing; Result is also shown in Table X.
Result shown in Table I X-X highlights the advantage of this pair of flocculating agent process.Embodiment 12,14-16 describe the shear stability of the improvement shown by lower percent by volume being less than the particle of 10 microns by size.Find that these samples are better than embodiment 11 and 13.
Table VIII. calcium carbonate types, the flocculant of embodiment describe and flocculant dose.
Table I X. 800rpm preparation and at 1500 rpm follow-up shear time the feature of calcium carbonate sample of flocculation of embodiment 11-12
Table X. the feature of the flocculation calcium carbonate sample in embodiment 13-16.
At least one embodiment is that pre-flocculation is by the method for the filler of high electric charge, low molecular weight, anionic dispersing agents dispersion.The method is made up of the following step: water-based slurry a) providing the filler particles of anionic dispersant; B) in this dispersion, low molecular weight coagulating agent is added, to neutralize the electric charge in this system wholly or in part; C) under the condition of highly mixing, in this dispersion, the first flocculant is added; D) under the condition of highly mixing, the second flocculant (can be coagulating agent or flocculating agent) is added to this dispersion; And e) optionally, shear the dispersion of this flocculation, to provide the dispersion of the filler flocculate with desired particle size.
As previously mentioned, preferably, this low molecular weight, in and the composition of electric charge be coagulating agent.Preferably, the first flocculant is anion or cationic flocculants, as previously mentioned.Preferably, the second flocculant has and the coagulating agent of the first flocculant opposite charges or flocculating agent.With reference to the following example 17-20, this can understand best:
embodiment 17-20
The calcium carbonate (GCC) ground for the dispersion of these embodiments is Hydrocarb HO G-ME or Omyafil 90 available from Omya.The GCC running water of the dispersion obtained as the slurry of 65% solid is diluted to 10% solid.Use with three seconds intervals during flocculating the size distribution of S400FBRM (Focused Beam Reflectance measurement) probe measurement filler, as described in embodiment 1-7.Laser microprobe is inserted in the 600mL beaker of the 10%PCC slurry containing 300mL.Before adding flocculant, stir this solution at least 30 seconds with IKA RE16 stirring motor with 800rpm.
In slowly adding in the process of about a few minutes and polymer.Then the first flocculant syringe is slowly added in the process of a few minutes.When use the second flocculant, wait for ten seconds with make first flocculant mixing after, add the second flocculant in the mode similar to the first flocculant.Then this slurry is stirred 2 to 4 minutes at 1500rpm, to test filler flocculate stability under high shear conditions..
Source, the flocculant of the calcium carbonate ground of Table X I. embodiment 17-20 describe and flocculant dose.
Table X II. 800rpm preparation and at 1500 rpm follow-up shear time the feature of the calcium carbonate sample ground of flocculation of embodiment 17-20.
Ex In the time of 1500rpm D(v,0.1) D(v,0.5) D(v,0.9) Vol％<10um Span
17 0 12.2 35.1 113.2 5.2 2.9
18 0 59.9 139.5 235.9 0.0 1.3
19 0 24.9 101.8 211.9 2.1 1.8
20 0 27.4 77.4 171.3 0.3 1.9
? ? ? ? ? ? ?
17 2mins. 8.4 21.5 62.6 14.0 2.5
18 2mins. 34.7 74.2 148.7 0.6 1.5
19 2mins. 7.5 36.1 130.6 13.9 3.4
20 2mins. 18.4 45.3 101.9 1.4 1.8
? ? ? ? ? ? ?
18 4mins. 27.6 57.6 46.8 0.7 0.3 (here, mistake)
20 4mins. 14.6 35.9 84.2 3.2 1.9
? ? ? ? ? ? ?
18 8mins. 22.6 46.9 91.7 0.7 1.5
As shown in Table X I, embodiment 18 and 20 illustrates disclosed the present invention, that is, by the initial treatment of charging neutrality polymer, next with two kinds of flocculating polymer process.Embodiment 17 and 19 represents after coagulating agent uses and uses flocculating agent.As shown in Table X II, in embodiment 18 and 20, pre-flocculated GCC presents the shear stability of improvement, and this is shown by median particle diameter D (v, 0.5) larger under shearing in equivalent.Embodiment 18 and 20 also has the domain size distribution of improvement, and this is by less span and the more small size percentages show being less than 10 microns.
embodiment 21
The object of these embodiments evaluates the pre-flocculated calcium carbonate ground to the impact of paper physical character.The pre-flocculation sample of embodiment 20 is used for this object, and compares with untreated Omyafil90.
The thick stock of denseness 2.3% is prepared from the cork dry pulp plate (softwood dry lap pulp) of 75% hardwood dry pulp plate (hardwood dry lap pulp) and 25%.This hardwood and cork are refined the freedom into 400mL Canadian Standard Freeness (tappi test method T 227om-94) in Valley beater (available from Voith Sulzer, Appleton, WI).With running water, this thick stock is diluted to 0.5% denseness.
In dynamic drainage instrument, prepare handmade paper with the batching of 0.5% denseness of 800rpm mixing 650mL, the end sieve that the useful plastic solidification sheet of this dynamic drainage instrument band covers is to prevent drainage.Dynamic drainage instrument and blender can available from Paper Chemistry Consulting Laboratory, Inc., Carmel, NY.Start mixing, add GCC sample, then Nalco 7542 sizing agent (sizing agent) of 11 pounds of/ton of cationic starches and 3 pounds/ton was added at 15 seconds, it is that the sodium acrylate-acrylamide copolymer flocculating agent of 29mol% (can from Nalco Company that the RSV finally adding 0.6 pound/ton (based on product) is about 32dL/g and charge content, Naperville, IL obtain).
Stopped mixing at 45 seconds, batching is transferred in the deckle box of Noble & Wood handsheet mold.By 100 order forming net drainages, thus form the handmade paper of 8 " × 8 ".By two blotting paper and metallic plate to be put on wet handmade paper and by the roll-in of 25 pounds of metallic roll six times, by handmade paper from the pressing of paper mould net.Remove forming net and a blotting paper, this handmade paper is put between two new blotting paper and press felt, and suppresses with 50psig with plane press.Remove all blotting paper, with being set as the drumdrier of 220 °F this handmade paper dry 60 seconds (end face is in the face of drying machine surface).Handsheet mold, roll press and drumdrier can available from Adirondack Machine Company, Glens Falls, NY.To the PCC sample of often kind of test, prepare five parts of handmade paper duplicate.
The handmade paper of finished product is store overnight under the TAPPI standard conditions of 50% relative humidity and 23 DEG C.Measure the basic weight (tappi test method T 410om-98) of handmade paper, measure its content of ashes (tappi test method T 211om-93) to determine PCC content, measure its brightness (ISO method of testing 2470:1999), measure its opacity (ISO method of testing 2471:1998), measure its evenness, TENSILE STRENGTH (tappi test method T 494om-01), Scott bond strength (tappi test method T 569pm-00) and z-to TENSILE STRENGTH (ZDT, tappi test method T 541om-89).With available from Metso Automation, Helsinki, FI's formation analyzer measures formation of sheet (measuring of basis weight uniformity).
Table X II. comprises the character of the paper of the pre-flocculation sample described in the untreated calcium carbonate that grinds or embodiment 20.
Mechanical strength data in Table X II show, compared with comprising the paper of untreated GCC, paper its tensile figure under the ash level of 18% comprising the pre-flocculation filler of preparation in embodiment 20 increases 20%, and internal bond strength increases 10%.
Although the present invention can implement by many different forms, describe concrete preferred embodiment of the present invention in this article in detail.Present disclosure is the example of principle of the present invention, instead of intends to limit the invention to shown particular.All patents mentioned in this article, patent application, scientific literature and other bibliography any are incorporated in this entirety by reference.In addition, the combination of any possible some or all of various embodiments that are that describe in this article and/or that introduce in this article is contained in the present invention.In addition, the present invention is contained and get rid of any one or some any possible combination in various embodiments that are described herein and/or that introduce especially herein.
Above-mentioned disclosure is intended to illustrate, and non exhaustive.This description will enlighten many modification and alternative to those of ordinary skill in the art.All these alternative and modification all should be included in the scope of claims, and wherein term " comprises (comprising) " and referring to " comprise (comprising) but be not limited to ".Those of ordinary skill in the art can recognize that other of specific embodiments described herein is equivalent and substitute, these are equivalent substitute also to intend contain by claim.
Disclosed all scopes and parameter are all understood to include any and all subranges be included in wherein in this article, and any numerical value between end points.Such as, the scope of " 1 to 10 " of pointing out be believed to comprise any and all subranges between minimum of a value 1 and maximum 10 (and comprising minimum of a value 1 and maximum 10); Namely, from minimum of a value more than 1 (such as 1 to 6.1), and with the subrange (such as 2.3 to 9.4,3 to 8 that maximum less than 10 stops,, and final for being included in the numerical value 1,2,3,4,5,6,7,8,9 and 10 within the scope of this 4 to 7).
This accomplishes the description of preferred and alternative embodiment of the present invention.Those skilled the in art will appreciate that the equivalent of specific embodiment described herein substitutes, and described equivalent substitute to intend contain by appended claim.

Claims (10)

1., for the preparation of the method with the stabilising dispersions of the flocculation filler particles of specified particle diameter distribution of paper technology, described method comprises:
A) water-borne dispersions of filler particles is provided;
The amount that b) described filler particles can not be caused significantly to flocculate to be enough to Homogeneous phase mixing in described dispersion adds the first flocculant in described dispersion, and described first flocculant is both sexes;
C) to be enough to cause the flocculation of described filler particles under described first flocculant exists
Amount adds the second flocculant in described dispersion, and wherein said second flocculant is with the electric charge contrary with the net charge of the first amphoteric flocculating agent;
D) dispersion of flocculating is sheared to provide the dispersion of the filler flocculate with required particle diameter; With
E) before adding in paper stock by filler particles, make their flocculations and wherein during flocculating, there is not paper stock.
2. the process of claim 1 wherein that described filler flocculate has the median particle diameter of 10-100 μm.
3. the process of claim 1 wherein calcium carbonate, the calcium carbonate ground, kaolinton, talcum, titanium dioxide, hibbsite, barium sulfate and magnesium hydroxide that described filler is selected from precipitation and their mixture.
4. the process of claim 1 wherein that described first flocculant has clean anionic charge.
5. the method for claim 4, wherein said second flocculant is cationic, be selected from copolymer and the trimer of (methyl) acrylamide and dimethylaminoethyl methacrylate (DMAEM), dimethylaminoethyl acrylate (DMAEA), acrylic acid lignocaine ethyl ester (DEAEA), diethylaminoethyl methacrylate (DEAEM) or their quaternary ammonium form, with their mixture, prepared by wherein said quaternary ammonium form dimethyl suflfate, chloromethanes or chlorotoluene.
6. the method for claim 5, wherein said second flocculant has the cationic charge of 10-50 % by mole and the acrylamide and acrylic acid dimethylaminoethyl chloromethanes season copolymer of at least RSV of 15dL/g.
7. the method for claim 4, wherein said second flocculant is the diallyldimethylammonium chloride homopolymers of the RSV with 0.1-2dL/g.
8. the method for claim 1, is also included in the dispersion of the backward described flocculation of interpolation second flocculant and adds one or more particulates.
9. the process of claim 1 wherein that filler is anionic dispersant and low-molecular-weight cationic coagulant was added to before interpolation first flocculant in described dispersion with at least partly and its anionic charge.
10. comprise the papermaking process using filler, said method comprising the steps of:
The water-borne dispersions of filler particles, at least one dry strength auxiliary agent and cellulose fibre raw material are provided,
With filler particles described in the compositions-treated of material,
Filler particles is combined with described cellulose fibre raw material,
With bond described in the process of at least one dry strength auxiliary agent, and
Paper felt is formed by described bond,
At least 10% of wherein said filler particles uses high anionic charge dispersant and in the form of disperseing, described cellulose fibre raw material packet is containing multiple cellulose fiber peacekeeping water, and the composition of described material improves the performance of the dry strength auxiliary agent in described paper felt.
CN201380019024.5A 2012-04-18 2013-04-18 Controllable filler prefloculation using a dual polymer system Pending CN104271836A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109074033A (en) * 2016-04-01 2018-12-21 凯米罗总公司 For optimizing cohesion and/or flocculated method and system in water treatment procedure
CN109629333A (en) * 2019-01-26 2019-04-16 邱振权 A kind of filler pre-treatment method for paper technology
CN110240244A (en) * 2019-05-20 2019-09-17 南京金陵化工厂有限责任公司 A kind of settlement treatment pond of chemical industrial organic wastewater and its flocculating agent
CN111074673A (en) * 2019-12-09 2020-04-28 宁波亚洲浆纸业有限公司 Method for treating filler for papermaking and papermaking method
CN113736014A (en) * 2021-08-24 2021-12-03 苏州欧亦博工业科技有限公司 Pre-flocculant for papermaking filler and preparation method

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3018175B1 (en) 2014-11-07 2019-02-06 Omya International AG A process for the preparation of flocculated filler particles
EP3018176B1 (en) 2014-11-07 2018-04-25 Omya International AG A process for the preparation of flocculated filler particles
CZ29098U1 (en) * 2014-12-17 2016-02-01 Univerzita Palackého v Olomouci Composite planar cellulose-based material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6287414A (en) * 1985-10-14 1987-04-21 Oji Paper Co Ltd Method of treating ground limestone for paper making
US4749444A (en) * 1985-11-21 1988-06-07 Basf Aktiengesellschaft Production of paper and cardboard
EP0752496A2 (en) * 1995-07-07 1997-01-08 Eka Chemicals AB A process for the production of paper
JP2010121247A (en) * 2008-11-21 2010-06-03 Oji Paper Co Ltd Porous filler and method for producing the same
WO2010126712A1 (en) * 2009-04-28 2010-11-04 Nalco Company Controllable filler prefloculation using a dual polmer system
US20110226433A1 (en) * 2007-09-12 2011-09-22 Weiguo Cheng Method of increasing filler content in papermaking

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609431A (en) * 1984-07-26 1986-09-02 Congoleum Corporation Non-woven fibrous composite materials and method for the preparation thereof
US6033524A (en) * 1997-11-24 2000-03-07 Nalco Chemical Company Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment
US6835282B2 (en) * 1998-10-16 2004-12-28 Grain Processing Corporation Paper web with pre-flocculated filler incorporated therein
US8172983B2 (en) * 2007-09-12 2012-05-08 Nalco Company Controllable filler prefloculation using a dual polymer system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6287414A (en) * 1985-10-14 1987-04-21 Oji Paper Co Ltd Method of treating ground limestone for paper making
US4749444A (en) * 1985-11-21 1988-06-07 Basf Aktiengesellschaft Production of paper and cardboard
EP0752496A2 (en) * 1995-07-07 1997-01-08 Eka Chemicals AB A process for the production of paper
US20110226433A1 (en) * 2007-09-12 2011-09-22 Weiguo Cheng Method of increasing filler content in papermaking
JP2010121247A (en) * 2008-11-21 2010-06-03 Oji Paper Co Ltd Porous filler and method for producing the same
WO2010126712A1 (en) * 2009-04-28 2010-11-04 Nalco Company Controllable filler prefloculation using a dual polmer system

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109074033A (en) * 2016-04-01 2018-12-21 凯米罗总公司 For optimizing cohesion and/or flocculated method and system in water treatment procedure
US10988392B2 (en) 2016-04-01 2021-04-27 Kemira Oyj Method and system for optimization of coagulation and/or flocculation in a water treatment process
CN109074033B (en) * 2016-04-01 2022-04-19 凯米罗总公司 Method and system for optimizing coagulation and/or flocculation in water treatment processes
CN109629333A (en) * 2019-01-26 2019-04-16 邱振权 A kind of filler pre-treatment method for paper technology
CN110240244A (en) * 2019-05-20 2019-09-17 南京金陵化工厂有限责任公司 A kind of settlement treatment pond of chemical industrial organic wastewater and its flocculating agent
CN111074673A (en) * 2019-12-09 2020-04-28 宁波亚洲浆纸业有限公司 Method for treating filler for papermaking and papermaking method
CN111074673B (en) * 2019-12-09 2022-06-07 宁波亚洲浆纸业有限公司 Method for treating filler for papermaking and papermaking method
CN113736014A (en) * 2021-08-24 2021-12-03 苏州欧亦博工业科技有限公司 Pre-flocculant for papermaking filler and preparation method

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EP2839076A1 (en) 2015-02-25
KR20150008125A (en) 2015-01-21

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