WO2022269127A1 - Système d'agent de rétention et composition pour fabrication de papier, et procédé de fabrication de papier - Google Patents

Système d'agent de rétention et composition pour fabrication de papier, et procédé de fabrication de papier Download PDF

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Publication number
WO2022269127A1
WO2022269127A1 PCT/FI2022/050409 FI2022050409W WO2022269127A1 WO 2022269127 A1 WO2022269127 A1 WO 2022269127A1 FI 2022050409 W FI2022050409 W FI 2022050409W WO 2022269127 A1 WO2022269127 A1 WO 2022269127A1
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WO
WIPO (PCT)
Prior art keywords
starch
retention agent
agent system
retention
component
Prior art date
Application number
PCT/FI2022/050409
Other languages
English (en)
Inventor
Jonni Ahlgren
Jaakko Hiltunen
Original Assignee
Kemira Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kemira Oyj filed Critical Kemira Oyj
Publication of WO2022269127A1 publication Critical patent/WO2022269127A1/fr

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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
    • 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
    • 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
    • D21H17/29—Starch cationic
    • 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

Definitions

  • the present invention relates to a retention agent system for making of paper, board or the like.
  • the present invention also relates to a use of a retention agent system for making of paper, board or the like.
  • the present invention further relates to a papermaking composition comprising a retention agent system.
  • the present invention also relates to a method for producing paper, board or the like.
  • Retention agents are available, and they can be added to the fi bre stock in order to improve the retention of additives, fibre fines, disturbing sub stances, etc. to the cellulosic fibres and to the formed web.
  • Retention agents are usually synthetic or semi-synthetic polymeric compounds. Use of synthetic poly mers increases the costs, which is not preferred when cheaper grades of paper and board are produced. Consequently, there is a need for new effective retention sys tems, which would be more sustainable, economically competitive and produce good quality end product.
  • Typical main retention aid is synthetic cationic polyacrylamide.
  • the cationic polyacrylamide has an average molecular weight of 5000 -20000 Da. The magnitude of molecular size may also be stated as standard viscosity.
  • Retention grade polyacrylamides have typically standard vis cosity (SV), also called UL viscosity, >2 mPas, and charge density is 0.2 - 2.5 meq/g.
  • Cationic starches are also well-known agents in papermaking. They are mainly used in the wet end of the paper machine, where they are added to the fibre stock before the paper machine headbox. The main aim for wet end starch use is to improve dry strength, and as wet end starches have low cationic charge, they may have positive impact on retention, but they are not efficient enough as reten tion agent.
  • cationic wet end starches for dry strength are normally in powder form and their degree of substitution (DS) is clearly ⁇ 0.1, i.e. they are low cationic starches.
  • Low cationic starch is not soluble in water without cooking.
  • Cooking means that temperature of water, in which the starch particles form a dispersion, is raised above gelatinization temperature of starch.
  • Gelatinization temperature is starch type specific, and varies typically between 60-85 °C. For most of the starches cooking at 90-100 °C is enough.
  • Jet cooking starch mixture is introduced into a jet cooker with steam.
  • the cooking temperature in the cooker varies between 120 — 160 °C, depending on the starch type.
  • a typical method for producing paper, board or the like comprises at least following steps:
  • Performance of cationic starch (alone) in retention is not as good as per formance of CPAM (cationic polyacrylamide).
  • CPAM cationic polyacrylamide
  • High molecular weight (MW) starch helps in performance, but different MWs are needed in different applications.
  • Cationic starches which have degree of substitution (DS) of at least 0.15 are considered high cationic starches and they are relatively soluble in water with out cooking agent.
  • cationic starch can be dissolved without cooking a blend of cat ionic starch and CPAM can be used (CPAM cannot be cooked).
  • water soluble starch refers to starches which dis solve in room temperature in water at least partly, increasing viscosity signifi cantly, though turbidity may remain higher than when cooking is made.
  • High cationic starches give better retention efficiency than low cationic starches, but still their retention efficiency is clearly lower than retention efficiency of cationic polyacrylamides.
  • Standard viscosity is measured at 0.1 weight-% polymer content in an aqueous 1 M NaCl solution using Brookfield LV viscometer equipped with UL adapter, at 25 °C, using UL Adapter Spindle and rotational speed 60 rpm.
  • Cationic acrylamide polymer comprises a copolymer of (methacryla mide and at least one cationic monomer.
  • the copolymer of (meth) acrylamide, pref erably acrylamide, and at least one cationic monomer may be obtained by copoly merisation of (meth) acrylamide and 5 - 50 mol%, preferably 6-40 mol%, more preferably 8 - 25 mol%, of cationic monomer(s).
  • the at least one cationic monomer in the synthetic cationic copolymer of (meth) acrylamide may be selected from a group of 2-(dimethylamino)ethyl acrylate (ADAM), [2-(acryloyloxy)ethyl] trimethylammonium chloride (ADAM-C1), 2-(dimethylamino)ethyl acrylate benzylchloride, 2-(dimethylamino)ethyl acrylate dimethylsulphate, 2 -dimethylaminoethyl methacrylate (MADAM), [2-(methacrylo- yloxy) ethyl] trimethylammonium chloride (MADAM-C1), 2-dimethylaminoethyl methacrylate dimethylsulphate, [3 -(acryloylamino) propyl] trimethylammonium chloride (APTAC), [3 -(methacryloylamino) propyl] trimethyl
  • the cationic polyacrylamide is in a form of particles, like beads or dry powder.
  • the cationic polymer may be obtained by solution polymerisation, sus pension polymerisation, or gel polymerisation.
  • An object of the present invention is thus to provide a retention agent system and a papermaking composition comprising said retention agent system so as to overcome the problems in prior art.
  • a further object of the present invention is to provide a use of said re tention agent system in papermaking and board making.
  • a still further object of the present invention is to provide a method for producing paper, board or the like.
  • the retention agent system for making of paper, board or the like comprises a component (A) and a component (B), wherein component (A) is a water soluble, high cationic starch having a degree of substitu tion (DS) of at least 0.15, and component (B) is a very high molecular weight cationic polyacrylamide (CPAM), having a SV viscosity of at least 4 mPas, preferably in the range of 4.0-7.0 mPas, the weight ratio of A:B being in the range of 80:20-20:80.
  • component (A) is a water soluble, high cationic starch having a degree of substitu tion (DS) of at least 0.15
  • component (B) is a very high molecular weight cationic polyacrylamide (CPAM), having a SV viscosity of at least 4 mPas, preferably in the range of 4.0-7.0 mPas, the weight ratio of A:B being in the range of 80:20-20:80
  • the retention agent system has a viscosity, in a solution concentration of 0.5%, in the range of 10 - 1000 mPas, more preferably 50 - 500 mPas, measured at 25 °C with Brookfield LV- viscometer, in small sample adapter, spindle SC4-18.
  • the cationic starch (A) is made from a starch selected from a group comprising potato starch, waxy potato starch, rice starch, corn starch, waxy corn starch, wheat starch, barley starch, sweet potato starch, tapioca starch, pea starch and any of their mixtures.
  • the cationic starch in the retention agent system has a degree of substitution, DS, in the range from 0.15 to 1.0, preferably from 0.15 to 0.7, more preferably from 0.15 to 0.5, more prefera bly from 0.15 to 0.3, most preferably 0.15-0.22.
  • the cationic starch is non-degraded and/or free of cross-linkages.
  • the retention agent system of the invention preferably has a weight ra tio of A:B in the range of 50:50-30:70.
  • the present invention also provides a use of a retention agent system according to the invention in papermaking and board making or the like.
  • the retention agent is preferably used in com bination with at least one type of microparticles, or at least one type of other reten tion agents, or a combination thereof.
  • the present invention further provides a papermaking composition comprising a retention agent system according to the invention.
  • the papermaking composition ac cording to the invention further comprises at least one type of microparticles, or at least one type of other retention agents, or a combination thereof.
  • the present invention further provides a method for producing paper, board or the like, comprising at least following steps:
  • component (A) is a water soluble, high cationic starch having a degree of substitution (DS) of at least 0.15
  • component (B) is a very high molecular weight cationic polyacrylamide (CPAM), having a SV viscosity of at least 4 mPas, preferably in the range of 4.0-7.0 mPas, the weight ratio of A:B being in the range of 80:20-20:80,
  • CPAM very high molecular weight cationic polyacrylamide
  • component (A) and component (B) are in the form of a blend in particle or solid form, such as powder form which is dissolved, and if necessary, diluted before adding to fibre stock.
  • component (A) and component (B) are mixed as dry particles into a blend, using e.g. a mechanical mixer, or, the flows of the dry particles are combined upon packaging before said dry particles introduced into a sack or bag.
  • the invention is based on the finding that by combining a very high MW CPAM, and a cationic starch a retention agent system showing a retention response close to that of a standard MW CPAM is obtained, while at the same time, sustaina bility of the retention agent system is increased, because less fossil carbon needs to be used as starch is used instead of CPAM.
  • high cationic starches which can be dissolved in water without cooking, and give reasonable retention efficiency, give possibility to reduce fossil carbon content in retention agent systems.
  • retention efficiency of the retention agent system decreases. But the decrease in the retention efficiency can be avoided, if the high cationic starch is used together with a cationic poly acrylamide having higher molecular weight than the standard cationic polyacryla mide.
  • Each re tention performance test was performed on a 1:1 blend of pine and birch. Dosing sequence was as follows: retention polymer dosing at 10 s, microparticle dosing at 30 s. Polymer retention was estimated from floe size at 20 s and microparticle re tention from the floe size at 40 s.
  • Retention performance of a variety of different blends of a cationic starch and a cationic polyacrylamide (CPAM) was tested by using focused beam reflectance measurement (FBRM).
  • the method follows floe size development and is comparable to retention. Retention performance is estimated with the floe size at certain time after polymer dosing.
  • FBRM Focused Beam Reflectance Measurement
  • Used FBRM apparatus is Lasentec FBRM Model D600L by Laser Sensor Technology, Redmond, WA, USA, Serial No. 1106, and its detector is D600L-HC22- K, Serial No. 961.
  • the FBRM instrument is a flocculation analyzer using a highly focused laser beam and back-scattered geometry as a principle of operation. From the collected data the FBRM instrument yields chord length distribution, mean of the chord length values and the number of particles detected. The measurement range of the device is 1 - 1000 gm.
  • Mean of the chord length value is used as the relative value for retention performance.
  • Turbidities were measured using HACH, 2100 AN IS Laboratory Turbi dimeter.
  • the pulp used was a mixture of refined chemical pulps of pine and birch in ratio 1:1.
  • the tests were used as FBRM tests in a beaker. Amount of furnish in a test was 500 g. The furnish was continuously mixed using an overhead stirrer and a propeller impeller at 1500 rpm. The test polymer was dosed, and the mean chord length value was taken 10 s after polymer dosing. Starch used was Hi-Cat 1574A from Roquette. The other polymers used were cationic polyacrylamides (CPAM). CPAM1 was a 9 mol-% with Standard Vis cosity (SV) 4.8 mPas. SV is defined as viscosity of 0.1 % polymer solution in 1 M NaCl measured using Brookfield viscometer and UL adapter 60 rpm and at 25 °C. CPAM2 was 9 mol-% with SV 3.4 mPas. The polymers were used as 0.1 % solutions. The dissolutions were made at room temperature; no cooking for starch was done.
  • Retention testing results are shown in Table 3.
  • the dosage is expressed as g or kg per dry matter of the furnish.
  • Table 3. Comparison of retention test results with CPAM2 and with combinations of starch and different CPAMs at different dosage levels. Mean chord length values taken 10 s after polymer dosing (gm). At lower dosages a combination of starch and a CPAM having high enough SV value performs about equally to a pure CPAM having lower SV value, and at higher dosages the performance is even better.
  • starch 1574A performs slightly better than starch PAF#9152ER, but combinations of both starches with a CPAM having high enough SV value perform about equally or better to a CPAM having lower SV value.
  • CPAM3 was used instead of CPAM2 another CPAM; CPAM3 was a 9 mol-% with SV 3.3 mPas
  • Example 4 The tests were made using the same furnish as in Example 4. The poly mers were dosed in similar manner, but also a microparticle was used in the reten tion program.
  • the microparticle used was FennoSil 5000 from Kemira. Its dosage was 2 kg/t and it was dosed 20 s after the polymer dosing. The mean chord length value was taken 10 s after microparticle dosing.
  • Viscosity effect of high cationic starch in a retention agent blend was tested by comparing viscosities of blends to viscosities of pure polyacrylamides.
  • the starch used was the same as in Example 2, Hi-Cat 1574A (1574A). It was blended with the same CPAM1 polyacrylamide as in Example 2.
  • the other poly acrylamide, CPAM2 was also the same used in Example 2.
  • the blends tested were 1574A+CPAM1 in ratio 50/50 and in ratio
  • Viscosities were measured using Brookfield LV viscometer, equipped with Small Sample Adapter, at 25 °C, using spindle SC4-18 and always the highest rotation speed allowed (max 60 rpm). The results are shown in Table7.
  • the viscosity comparison tells that viscosity of a high cationic starch and very high MW polyacrylamide is at about the same level or even lower.
  • a solution of a blend of starch and very high MW CPAM has a viscosity equal or lower than viscosity of a solution of standard MW CPAM.
  • Lower viscosity is a ben efit because higher polymer concentration can be used at the same viscosity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne un système d'agent de rétentions et une composition pour la fabrication de papier, ainsi qu'un procédé de fabrication de papier. Le système d'agent de rétention peut être utilisé comme agent de rétention dans la fabrication de papier et de carton. Le système d'agent de rétentions comprend un composant (A) et un composant (B). Le composant (A) est un amidon cationique, soluble dans l'eau, dont le degré de substitution (DS) est d'au moins 0,15. Le composant (B) est un polyacrylamide cationique (CPAM), dont la viscosité statique est d'au moins 4 mPa·s. Le rapport pondéral de A:B se situe dans la plage de 80:20 à 20:80.
PCT/FI2022/050409 2021-06-22 2022-06-13 Système d'agent de rétention et composition pour fabrication de papier, et procédé de fabrication de papier WO2022269127A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20215733 2021-06-22
FI20215733 2021-06-22

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Publication Number Publication Date
WO2022269127A1 true WO2022269127A1 (fr) 2022-12-29

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008095769A1 (fr) * 2007-02-05 2008-08-14 Basf Se Fabrication de papier ou de carton
WO2013107933A1 (fr) * 2012-01-16 2013-07-25 Kemira Oyj Procédé de production de papier, carton ou analogue et aggloméré
WO2013140046A1 (fr) * 2012-03-23 2013-09-26 Kemira Oyj Procédé de dissolution d'amidon cationique, agent de fabrication de papier et son utilisation
WO2018055239A1 (fr) * 2016-09-26 2018-03-29 Kemira Oyj Composition à résistance à sec, son utilisation et procédé de fabrication de papier, de carton ou équivalent
WO2020012074A1 (fr) * 2018-07-12 2020-01-16 Kemira Oyj Procédé de fabrication d'une bande fibreuse multicouche et bande fibreuse multicouche
WO2020257978A1 (fr) * 2019-06-24 2020-12-30 Kemira Oyj Structure polymère et ses utilisations

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008095769A1 (fr) * 2007-02-05 2008-08-14 Basf Se Fabrication de papier ou de carton
WO2013107933A1 (fr) * 2012-01-16 2013-07-25 Kemira Oyj Procédé de production de papier, carton ou analogue et aggloméré
WO2013140046A1 (fr) * 2012-03-23 2013-09-26 Kemira Oyj Procédé de dissolution d'amidon cationique, agent de fabrication de papier et son utilisation
WO2018055239A1 (fr) * 2016-09-26 2018-03-29 Kemira Oyj Composition à résistance à sec, son utilisation et procédé de fabrication de papier, de carton ou équivalent
WO2020012074A1 (fr) * 2018-07-12 2020-01-16 Kemira Oyj Procédé de fabrication d'une bande fibreuse multicouche et bande fibreuse multicouche
WO2020257978A1 (fr) * 2019-06-24 2020-12-30 Kemira Oyj Structure polymère et ses utilisations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GERLI ET AL., APPITA JOURNAL, vol. 54, no. 1, January 2001 (2001-01-01), pages 36 - 40

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