CA1276413C - Papermaking process - Google Patents
Papermaking processInfo
- Publication number
- CA1276413C CA1276413C CA000505607A CA505607A CA1276413C CA 1276413 C CA1276413 C CA 1276413C CA 000505607 A CA000505607 A CA 000505607A CA 505607 A CA505607 A CA 505607A CA 1276413 C CA1276413 C CA 1276413C
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- CA
- Canada
- Prior art keywords
- sol
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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
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
Abstract
PAPERMAKING PROCESS
Abstract of the Disclosure:
In a process for making paper from an aqueous paper pulp, especially a pulp containing bleached/
unbleached mechanical pulps or unbleached chemical pulps, a combination of chemicals is added for improv-ing drainage and retention. As drainage- and retention-improving aids are added a cationic polyacrylamide and a sol of colloidal inorganic particles having at least one surface layer of aluminium silicate or aluminium-modified silicic acid.
Abstract of the Disclosure:
In a process for making paper from an aqueous paper pulp, especially a pulp containing bleached/
unbleached mechanical pulps or unbleached chemical pulps, a combination of chemicals is added for improv-ing drainage and retention. As drainage- and retention-improving aids are added a cationic polyacrylamide and a sol of colloidal inorganic particles having at least one surface layer of aluminium silicate or aluminium-modified silicic acid.
Description
~:7~i413 The present invention generally relates to a papermaking process in which an aqueous paper pulp containing cellulosic pu]p and, optionally, also mine-ral filler, is formed and dried, drainage- and reten-tion-improving chemicals being added to the paper pulp prior to Eorming.
Paper~aking processes of this general type are widely disclosed in the literature.
In the making of different grades of paper using bleached/unbleached mechanical pulps or unbleached chemical pulps, drainage and retention problems are normally encountered. This seems to be because when making special paper grades, high contents of detri-mental or trash substances are had in the paper stock.
These detrimental and trash substances consist of substances dissolved from the fibre, such as kraf-t lignin, lignosulphonates, hemicellulose, rosin and salts. In order to counteract the drainage and retention problems, it is possible to use various retention aids available on the market, but the effect of these aids is adversely affected by the detrimental or trash substances present in the stock. This is a well-known problem and has been discussed in the literature, for instance in the Swedish Paper Journal (Svensk Papperstidning) No. 14, 1979, pp. 408-413, and the Swedish Paper Journal ~o. 12, 1982, pp. 100-106. These basic works have shown that there is a reaction between e.g. anionic lignosulphonate and cationic retention ~ 27~3 aid, and that a so-called polyelectrolyte complex is formed. Such complexes often have an adverse ef-fect on -the drainability of the paper stock.
One ohject of the present invention therefore is to provide a drainage and retention systern which counteracts the drainage and retention problems en-coun-tered in papermaking, especially in the making of paper products based on bleached/unbleached mecha-nical pulps or unbleached chemical pulps. Another object of the invention is to provide a papermaking process providing satisfactory drainage and retention also when using such pulps.
Further objects and advantages of the invention will appear from the following specification and the accompanying drawings. Figs. 1-12 are diagrams of the results obtained in the Examples given below.
The invention is based on the surprising dis-covery that special cationic polymers, in combination with a special inorganic colloid, will give a substan-tial improvement in respect of drainage and retention on both mechanical and unbleached chemical pulps.
Quite generally, the system according to the invention comprises the step of admixing in the paper stock prior to forming a special combination of che-micals which comprise two components, one anionic and one cationic component. The anionic component is formed of colloidal particles having at least one surface layer of aluminium silicate or aluminium-modified silicic acid. The cationic component is formed of a cationic polyacrylamide. The characterizing features of -the invention are stated in the accompanying claims.
It is previously known to use combinations of anionic and cationic components in connection with papermaking. I'hus, European Patent EP-B-0,041,056 discloses a binder system where the fibres of the paper are bonded with the aid of a combination of cationic starch and silicic acid sol.
Another known method for improving the properties of a paper product is disclosed in EP-B-0,080,986 in which a binder system is formed of colloidal silicic acid and cationic or amphoteric guar gum.
In a development not yet published of the binder systems disclosed in -the last-mentioned two patent specifications, use is made of a special inorganic sol which is an aluminium silicate sol or an aluminium-modified silicic acid sol (Swedish patent applica-tion 8403062-6). This special sol has been found to give a particularly notable improvement in the function of the binder. An aluminium oxide-modified silicic acid sol as such has previously been used in connection with papermaking but not in combination with cationic substances. This appears from Swedish patent application 7900587-2.
European patent EP-B-0,020,316 discloses a surface-modified pigment having a surface coating in the form of two layers where one layer consists of an Al2O3-SiO2 hydrate gel and the other layer consists of a poly-meric binder. As examples of polymeric binders arestated e.g. polyacrylate and cationic polyamides.
This patent specification however relates to a pigment and aims at improving the properties of the pigment as an additive in paper or paints. The patent specifi-cation is not concerned with modifying the drainage and retention characteristics of a paper pulp.
Finnish Patents FI-C-67,735 and FI-C-67,736 disclose a three-component system for hydrophobic sizing of paper, which comprises a sizing agent, a cationic polymer and an anionic polymer. Examples of sizing agents are rosin acid, activated rosin acid, alkyl ketene dimer, carbamoyl chloride, succinic anhydride, fatty acid anhydride or fatty acid chloride. Examples of cationic polymers are cationic starch, cationic guar gum, poly-acrylamide, polyethylene imine, polyamine or polyamide amine. Examples of anionic polymers are colloidal silicic acid, bentonite, carboxymethyl cellulose or carboxylated polyacrylamide. The Examples stated in the patent specifications use bleached sulphate pulp as fibre material in the stock, for which reason the amount of detrimental or trash substances is small.
Nothing is mentioned in the patent specifications about the influence of the trash substances on the papermaking process. A preferred pH range of 6-8 is stated, which is in contradistinction to the present invention yielding good results within the entire pH range and, thus, also on the acid side, which is ~-~7~13 of importance when using mechanical stocks and other stocks having a hi.gh content of detrimental or trash subs-tances.
The known two-component systems based on one anionic and one cationic component thus mainly serve as binders and have yielded good results on most paper-making stocks, Eor instance an .increased bonding strength of the finished paper. Also, it is possible in some cases on e.g. wood-containing printing papers to obtain an increase in strength by means of such systems, especially with the system using guar gum and colloidal silicic acid.
It has however been found that these known systems are not fully effective for solving the drainage and retention problems in all types of papermaking stocks.
This is particularly notable in stocks containing bleached/unbleached mechanical or unb].eached chemical pulps. As mentioned above, this seems to be because cationic starch and cationic or amphoteric guar gum presumably has a tendency to react by preference with the dissolved wood or trash substances, such that the yield of the desi.red reaction with the inorganic sol is reduced.
If, as in the invention, the ca-tionic starch or the guar gum is replaced by cationic pol.yacrylamide and the inorganic colloid is a sol the particles of which have at least one surface layer of aluminium silicate or aluminium-modified silicic acid, as indi-cated above, there is however obtained a considerablyhigher reaction selectivity to the anionic inorganic colloid, also at high contents of trash substances, especially dissolved wood substances. As will appear from the following Examples, -this improvement is ex-tremely rnanifest.
The greatest improvements obtained with the in-vention have been observed ~hen the system is used for mechanical pulps or unbleached chemical pulps.
However, improvements are also obtained for other types of pulps, such as chemical pulp, e.g. sulphate or sulphite pulp from both hardwood and softwood.
The improvements with thermomechanical and mechanical pulps are highly significant. As used herein, the term "cellulosic pulp" and "cellulosic Eibres" re-fer to all types of paper stocks containing chemical pulp, thermomechanical pulp, chemi-thermomechanical pulp, refiner mechanical pulp and groundwood pulp.
The pulp from which the paper is formed may in-clude mineral fillers of conventional types, such as kaolin, bentonite, titanium dioxide, gypsum, chalk, and talc. As used herein, the term "mineral filler"
includes, in addition to these fillers, wollastonite and glass fibres and also mineral low-density fillers, such as expanded perlite. The mineral filler is usually added in the form of an aqueous slurry in the conven-tional concentrations used for such fillers.
As mentioned above, the mineral fillers in the paper may consist of or comprise a low-density or hiyh-bul.k filler. The possibility of adding such fil-lers to conventional paper stocks is limited by factors such as the drainage of the paper stock on the wire and the reten-tions of the fillers on the wire. It has been discovered that the problems caused by the addition of such fillers can also be counteracted or substantially elimi.nated by using the system ac-cording to -the present invention.
In the drainage and retention system according to the invention, the inorganic colloid should con-sist of colloidal particles having at least one sur-face layer of aluminium silicate or aluminium-modified silicic acid, such that the surface groups of the particl.es contain silicon atoms and aluminium atoms in a ratio of from 9.5:0.5 to 7.5:2.5. The particles of the sol should preferably have a surface area of 50-1000 m2/g and more preferably about 200-1000 m2/g, the best results having been observed when the surface area has been about 300-700 m2~g. The sol has advan-tageously been stabilized with an alkali. If the sol consists of an aluminium-modified silicic acid, the stabilization with alkali can be performed with an al]cali having a molar ratio of Sio2:M2o of from 10:1 to 300:1, preferably from 15:1 to 100:1 (M is an ion selected from the group consisting of Na, K, Li and NH4). It has been established that the colloidal sol 4~3 particles should have a size of less than 20 ~m (microns) and preferably an average particle size ranging from about 10 down to 1 ~m (a colloidal particle of aluminium-modified silicic acid having a surface area of about 550 m2/g corresponds to an average particle size of about 5 5 ~m)-If the colloidal particles consist of a purealuminium silicate sol, this can be prepared in a known manner by precipitation of water glass with sodium aluminate. Such a sol has homogeneous particles, such that the surfaces of the particles have silicon atoms and aluminium atoms in a ratio of 7.5:2.5. Alternatively, use can be made of an alumin1um-modified silicic acid sol, i.e. a sol in which only a surface layer of the surfaces of the sol particles contains both silicon and aluminium atoms. Such an aluminium-modified sol is prepared by modifying the surface of a silicic acid sol with aluminate ions, which is possible presumably because both aluminium and silicon may under suitable conditions assume the coordination number 4 or 6 in relation to oxygen, and because they both have approximately the same atomic diameter. Since the aluminate ion Al(OH)4 1 is geometrically identical with Si(OH)4, the ion can be inserted or substituted into the SiO2 surface, thus generating an aluminium silicate seat having a fixed negative charge. Such an aluminium-modified silicic acid sol is far more stable against gel formation within the pHrange4-6withinwhichunmodifiedsilicicacid ~L~J 7 f~ 3 sols may gel quickly, and is less sensitive to salt.
The production of aluminium-modified silicic acid sols is wel] known and disclosed in the literature, for exarnple in the book "The Chemistry of Silica"
by Ralph K. Iler, John Wiley & Sons, New York, 1979, pp. 407-410.
The modification of the silicic acid sol -thus implies that a given amount of sodium aluminate is caused to react at high pH (about 10) with the col-loida] silicic acid. This means that the colloidal particles will have surface groups that consist of _Al-OH . At low pH (4-6), these groups are strong-ly anionic in character. This is in contradistinction to a pure unmodified silicic acid sol where this strong anionic character is not obtained at low pH since silicic acid is a weak acid with PKS of about 7.
It has been found that the pH of the paper stock in a papermaking process according to the present invention is not particularly critical and may lie in a pH range of 3.5-10. Values higher than pH 10 and lower than pH 3.5 are however unsuitable. If, according to known technique, use is made of unmodified silicic acid as inorganic colloid, good results can be obtained only at high pH values within this interval, while in the present invention where use is made of aluminiurn silicate sol or aluminium-modified silicic acid sol, a satisfactory result is obtained within the entire pH range. A particular advantage of the ~.~7~3 present invention thus is that low pH below 7 or 6 can be used.
Other paper chemicals, such as size, alum and the like, can be used, but care must be taken to ensure that the contents of these substances do not become so excessive as to adversely affect the drainage- and retention-improving effects of the system according to the invention.
To achieve the object of the invention, the cationic polyacrylamide is added to the stock in an amount corresponding to 0.005-1.5% by weight, based on the dry substance of the stock. This content range also applies to the inorganic colloid. Lower addition levels do not seem to give any notable improvement, and higher addition levels do not seem to entail such improve-ment of drainage and retention as would justify the increased costs caused by the raised addition levels.
The invention will be described in more detail hereinbelow in some Examples.
In the Examples described hereinbelow, use was made of the following chemicals:
ORGANOSORB~ is a bentonite clay obtained from Allied Chemicals, Great Britain.
ORGANOPOL~ is an anionic polyacrylamide obtained from Allied Chemicals, Great Britain.
Different starch products BMB-190, a cationic starch having an N-content of 0.35%, obtained from Raisio AB, Sweden.
* trade mark BMB-165,a cationic starch having an N-content of 0.2%, obtained from Raisio AB, Sweden.
HKS, a high-cationised starch having an N-content of 1.75%.
SP-190, an amphoteric starch obtained from Raisio AB, Sweden.
SOLVITOSE~ N, a cationic starch having an N-content of 0.2%, obtained from AB Stadex, Malmo, Sweden.
SOLVITOSE~ D9, a cationic starch having an N-content of 0.75%, obtained from AB Stadex, Malmo, Sweden.
Amylopectin CATO 210, an amylopectin product having an N-content of 0.23%, obtained from Lyckeby-National AB, Sweden.
WAXI MAIZE*, an amylopectin product having an N-content of 0.31%, obtained from Laing National, Great Britain.
Polyimine POLYIMIN SK, obtained from BASF, West Germany.
POLYMIN, SN, obtained from BASF, West Germany.
Guar qum MEYPRoBOND3 120, an amphoteric guar gum, obtained from Meyhall AB, Switzerland.
MEYPROID~ 9801, a cationic guar gum product having an N-content of 2%, obtained from Meyhall AG, Switzer-land.
GENDRIV~ 158, a cationic guar gum product having an N-content of 1.43%, obtained from Henkel Corpora-tion, Minneapolis, Minnesota, USA.
* trade mark ~:7~
G~NDRIV~ 162, a cationic guar gum product having an N-content of 1.71~, obtained from Henkel Corpora-tion, Minneapolis, Minnesota, USA.
Polyacrylamide products PAM I* a polyacrylamide designated XZ 87431 obtained from Dow Chemical Rheinwerk GmbH, Reinmunster, West Germany and having a cationic activity of 0.22 meq/g and an approximate molecular weight of 5 million.
PAM II* a polyacrylamide designated XZ 87409 obtained from Dow Chemical Rheinwerk GmbH, Reinmunster, West Germany and having a cationic activity of 0.50 meq/g and an approximate molecular weight of 5 million.
PAM III, a polyacrylamide designated XZ 87410 obtained from Dow Chemical Rheinwerk GmbH, ReinmUnster, West Germany and having a cationic activity of 0.83 meq/g and an approximate molecular weight of 5 million.
PAM I~, a polyacrylamide designated XZ B7407 obtained from Dow Chemical Rheinwerk GmbH, ReinmUnster, West Germany and having a cationic activity of 2.20 meq/g and an approximate molecular weight of 5 million.
Polyethylene oxide POLYOX COAGULANT* a coagulant obtained from Union Carbide Corporation, USA.
POLYOX WSR 301, a polyethylene oxide product obtained from Union Carbide Corporation, USA.
Other roducts P
BUBOND 60, a low-molecular weight product having high cationic activity and obtained from Buckman Labo-ratories, USA
* trade mark 13 ~;27~,~13 BUBOND 65, a high-molecular weight product having high cationic activity and obtained from Buckman Labora-tories, USA.
BUFLOCK 171, a low-molecular weight product having high cationic activity and obtained from Buckman Laboratories, USA.
This Example relates to a drainage test using a Canadian Freeness Tester. The paper grade used was supercalendered magazine paper. The stock comprised 76% fibre and 24% filler (C-clay from English China Clay). The fibre fraction of the stock had the following composi~ion:
22% fully bleached pine sulphate pulp 15% dithionite-bleached thermomechanical pulp 35% groundwood pulp 28% broke.
The stock was taken from a commercial magazine papermaking machine and was diluted with white water from the same machine to a stock concentration of 3 g/l. The white water had a specific conductivity of 85 mS~m and a total organic content TOC = 270 mg/l.
The pH of the stock was adjusted to 5.5 with diluted sodium hydroxide solution. For different chemical dosages, the drainability of the stock was determined according to SCAN-C 21:65 in a Canadian Freeness Tester.
As inorganic sol, use was made of a 15% Al-silicic acid sol having a surface area of about 500 m2/g and * trade mark 14 a ratio of SiO2:Na2O of about 40 and 9% Al atoms on the sol particle surface which gives 0.46% on the total solids substance of the sol.
Tes-ts were carried out with both various polymers alone and various polymers combined with 0.3% inorganic sol, calculated on dry material. In the tests, 1000 ml of stock suspension was placed in a beaker having an agitator driven at a speed of 800 rpm ("Britt-jar").
In the tests with the various polymers alone, the Eollowing sequence of steps was used:
1. Addition of drainage and retention polymer to the stock suspension under agitation.
Paper~aking processes of this general type are widely disclosed in the literature.
In the making of different grades of paper using bleached/unbleached mechanical pulps or unbleached chemical pulps, drainage and retention problems are normally encountered. This seems to be because when making special paper grades, high contents of detri-mental or trash substances are had in the paper stock.
These detrimental and trash substances consist of substances dissolved from the fibre, such as kraf-t lignin, lignosulphonates, hemicellulose, rosin and salts. In order to counteract the drainage and retention problems, it is possible to use various retention aids available on the market, but the effect of these aids is adversely affected by the detrimental or trash substances present in the stock. This is a well-known problem and has been discussed in the literature, for instance in the Swedish Paper Journal (Svensk Papperstidning) No. 14, 1979, pp. 408-413, and the Swedish Paper Journal ~o. 12, 1982, pp. 100-106. These basic works have shown that there is a reaction between e.g. anionic lignosulphonate and cationic retention ~ 27~3 aid, and that a so-called polyelectrolyte complex is formed. Such complexes often have an adverse ef-fect on -the drainability of the paper stock.
One ohject of the present invention therefore is to provide a drainage and retention systern which counteracts the drainage and retention problems en-coun-tered in papermaking, especially in the making of paper products based on bleached/unbleached mecha-nical pulps or unbleached chemical pulps. Another object of the invention is to provide a papermaking process providing satisfactory drainage and retention also when using such pulps.
Further objects and advantages of the invention will appear from the following specification and the accompanying drawings. Figs. 1-12 are diagrams of the results obtained in the Examples given below.
The invention is based on the surprising dis-covery that special cationic polymers, in combination with a special inorganic colloid, will give a substan-tial improvement in respect of drainage and retention on both mechanical and unbleached chemical pulps.
Quite generally, the system according to the invention comprises the step of admixing in the paper stock prior to forming a special combination of che-micals which comprise two components, one anionic and one cationic component. The anionic component is formed of colloidal particles having at least one surface layer of aluminium silicate or aluminium-modified silicic acid. The cationic component is formed of a cationic polyacrylamide. The characterizing features of -the invention are stated in the accompanying claims.
It is previously known to use combinations of anionic and cationic components in connection with papermaking. I'hus, European Patent EP-B-0,041,056 discloses a binder system where the fibres of the paper are bonded with the aid of a combination of cationic starch and silicic acid sol.
Another known method for improving the properties of a paper product is disclosed in EP-B-0,080,986 in which a binder system is formed of colloidal silicic acid and cationic or amphoteric guar gum.
In a development not yet published of the binder systems disclosed in -the last-mentioned two patent specifications, use is made of a special inorganic sol which is an aluminium silicate sol or an aluminium-modified silicic acid sol (Swedish patent applica-tion 8403062-6). This special sol has been found to give a particularly notable improvement in the function of the binder. An aluminium oxide-modified silicic acid sol as such has previously been used in connection with papermaking but not in combination with cationic substances. This appears from Swedish patent application 7900587-2.
European patent EP-B-0,020,316 discloses a surface-modified pigment having a surface coating in the form of two layers where one layer consists of an Al2O3-SiO2 hydrate gel and the other layer consists of a poly-meric binder. As examples of polymeric binders arestated e.g. polyacrylate and cationic polyamides.
This patent specification however relates to a pigment and aims at improving the properties of the pigment as an additive in paper or paints. The patent specifi-cation is not concerned with modifying the drainage and retention characteristics of a paper pulp.
Finnish Patents FI-C-67,735 and FI-C-67,736 disclose a three-component system for hydrophobic sizing of paper, which comprises a sizing agent, a cationic polymer and an anionic polymer. Examples of sizing agents are rosin acid, activated rosin acid, alkyl ketene dimer, carbamoyl chloride, succinic anhydride, fatty acid anhydride or fatty acid chloride. Examples of cationic polymers are cationic starch, cationic guar gum, poly-acrylamide, polyethylene imine, polyamine or polyamide amine. Examples of anionic polymers are colloidal silicic acid, bentonite, carboxymethyl cellulose or carboxylated polyacrylamide. The Examples stated in the patent specifications use bleached sulphate pulp as fibre material in the stock, for which reason the amount of detrimental or trash substances is small.
Nothing is mentioned in the patent specifications about the influence of the trash substances on the papermaking process. A preferred pH range of 6-8 is stated, which is in contradistinction to the present invention yielding good results within the entire pH range and, thus, also on the acid side, which is ~-~7~13 of importance when using mechanical stocks and other stocks having a hi.gh content of detrimental or trash subs-tances.
The known two-component systems based on one anionic and one cationic component thus mainly serve as binders and have yielded good results on most paper-making stocks, Eor instance an .increased bonding strength of the finished paper. Also, it is possible in some cases on e.g. wood-containing printing papers to obtain an increase in strength by means of such systems, especially with the system using guar gum and colloidal silicic acid.
It has however been found that these known systems are not fully effective for solving the drainage and retention problems in all types of papermaking stocks.
This is particularly notable in stocks containing bleached/unbleached mechanical or unb].eached chemical pulps. As mentioned above, this seems to be because cationic starch and cationic or amphoteric guar gum presumably has a tendency to react by preference with the dissolved wood or trash substances, such that the yield of the desi.red reaction with the inorganic sol is reduced.
If, as in the invention, the ca-tionic starch or the guar gum is replaced by cationic pol.yacrylamide and the inorganic colloid is a sol the particles of which have at least one surface layer of aluminium silicate or aluminium-modified silicic acid, as indi-cated above, there is however obtained a considerablyhigher reaction selectivity to the anionic inorganic colloid, also at high contents of trash substances, especially dissolved wood substances. As will appear from the following Examples, -this improvement is ex-tremely rnanifest.
The greatest improvements obtained with the in-vention have been observed ~hen the system is used for mechanical pulps or unbleached chemical pulps.
However, improvements are also obtained for other types of pulps, such as chemical pulp, e.g. sulphate or sulphite pulp from both hardwood and softwood.
The improvements with thermomechanical and mechanical pulps are highly significant. As used herein, the term "cellulosic pulp" and "cellulosic Eibres" re-fer to all types of paper stocks containing chemical pulp, thermomechanical pulp, chemi-thermomechanical pulp, refiner mechanical pulp and groundwood pulp.
The pulp from which the paper is formed may in-clude mineral fillers of conventional types, such as kaolin, bentonite, titanium dioxide, gypsum, chalk, and talc. As used herein, the term "mineral filler"
includes, in addition to these fillers, wollastonite and glass fibres and also mineral low-density fillers, such as expanded perlite. The mineral filler is usually added in the form of an aqueous slurry in the conven-tional concentrations used for such fillers.
As mentioned above, the mineral fillers in the paper may consist of or comprise a low-density or hiyh-bul.k filler. The possibility of adding such fil-lers to conventional paper stocks is limited by factors such as the drainage of the paper stock on the wire and the reten-tions of the fillers on the wire. It has been discovered that the problems caused by the addition of such fillers can also be counteracted or substantially elimi.nated by using the system ac-cording to -the present invention.
In the drainage and retention system according to the invention, the inorganic colloid should con-sist of colloidal particles having at least one sur-face layer of aluminium silicate or aluminium-modified silicic acid, such that the surface groups of the particl.es contain silicon atoms and aluminium atoms in a ratio of from 9.5:0.5 to 7.5:2.5. The particles of the sol should preferably have a surface area of 50-1000 m2/g and more preferably about 200-1000 m2/g, the best results having been observed when the surface area has been about 300-700 m2~g. The sol has advan-tageously been stabilized with an alkali. If the sol consists of an aluminium-modified silicic acid, the stabilization with alkali can be performed with an al]cali having a molar ratio of Sio2:M2o of from 10:1 to 300:1, preferably from 15:1 to 100:1 (M is an ion selected from the group consisting of Na, K, Li and NH4). It has been established that the colloidal sol 4~3 particles should have a size of less than 20 ~m (microns) and preferably an average particle size ranging from about 10 down to 1 ~m (a colloidal particle of aluminium-modified silicic acid having a surface area of about 550 m2/g corresponds to an average particle size of about 5 5 ~m)-If the colloidal particles consist of a purealuminium silicate sol, this can be prepared in a known manner by precipitation of water glass with sodium aluminate. Such a sol has homogeneous particles, such that the surfaces of the particles have silicon atoms and aluminium atoms in a ratio of 7.5:2.5. Alternatively, use can be made of an alumin1um-modified silicic acid sol, i.e. a sol in which only a surface layer of the surfaces of the sol particles contains both silicon and aluminium atoms. Such an aluminium-modified sol is prepared by modifying the surface of a silicic acid sol with aluminate ions, which is possible presumably because both aluminium and silicon may under suitable conditions assume the coordination number 4 or 6 in relation to oxygen, and because they both have approximately the same atomic diameter. Since the aluminate ion Al(OH)4 1 is geometrically identical with Si(OH)4, the ion can be inserted or substituted into the SiO2 surface, thus generating an aluminium silicate seat having a fixed negative charge. Such an aluminium-modified silicic acid sol is far more stable against gel formation within the pHrange4-6withinwhichunmodifiedsilicicacid ~L~J 7 f~ 3 sols may gel quickly, and is less sensitive to salt.
The production of aluminium-modified silicic acid sols is wel] known and disclosed in the literature, for exarnple in the book "The Chemistry of Silica"
by Ralph K. Iler, John Wiley & Sons, New York, 1979, pp. 407-410.
The modification of the silicic acid sol -thus implies that a given amount of sodium aluminate is caused to react at high pH (about 10) with the col-loida] silicic acid. This means that the colloidal particles will have surface groups that consist of _Al-OH . At low pH (4-6), these groups are strong-ly anionic in character. This is in contradistinction to a pure unmodified silicic acid sol where this strong anionic character is not obtained at low pH since silicic acid is a weak acid with PKS of about 7.
It has been found that the pH of the paper stock in a papermaking process according to the present invention is not particularly critical and may lie in a pH range of 3.5-10. Values higher than pH 10 and lower than pH 3.5 are however unsuitable. If, according to known technique, use is made of unmodified silicic acid as inorganic colloid, good results can be obtained only at high pH values within this interval, while in the present invention where use is made of aluminiurn silicate sol or aluminium-modified silicic acid sol, a satisfactory result is obtained within the entire pH range. A particular advantage of the ~.~7~3 present invention thus is that low pH below 7 or 6 can be used.
Other paper chemicals, such as size, alum and the like, can be used, but care must be taken to ensure that the contents of these substances do not become so excessive as to adversely affect the drainage- and retention-improving effects of the system according to the invention.
To achieve the object of the invention, the cationic polyacrylamide is added to the stock in an amount corresponding to 0.005-1.5% by weight, based on the dry substance of the stock. This content range also applies to the inorganic colloid. Lower addition levels do not seem to give any notable improvement, and higher addition levels do not seem to entail such improve-ment of drainage and retention as would justify the increased costs caused by the raised addition levels.
The invention will be described in more detail hereinbelow in some Examples.
In the Examples described hereinbelow, use was made of the following chemicals:
ORGANOSORB~ is a bentonite clay obtained from Allied Chemicals, Great Britain.
ORGANOPOL~ is an anionic polyacrylamide obtained from Allied Chemicals, Great Britain.
Different starch products BMB-190, a cationic starch having an N-content of 0.35%, obtained from Raisio AB, Sweden.
* trade mark BMB-165,a cationic starch having an N-content of 0.2%, obtained from Raisio AB, Sweden.
HKS, a high-cationised starch having an N-content of 1.75%.
SP-190, an amphoteric starch obtained from Raisio AB, Sweden.
SOLVITOSE~ N, a cationic starch having an N-content of 0.2%, obtained from AB Stadex, Malmo, Sweden.
SOLVITOSE~ D9, a cationic starch having an N-content of 0.75%, obtained from AB Stadex, Malmo, Sweden.
Amylopectin CATO 210, an amylopectin product having an N-content of 0.23%, obtained from Lyckeby-National AB, Sweden.
WAXI MAIZE*, an amylopectin product having an N-content of 0.31%, obtained from Laing National, Great Britain.
Polyimine POLYIMIN SK, obtained from BASF, West Germany.
POLYMIN, SN, obtained from BASF, West Germany.
Guar qum MEYPRoBOND3 120, an amphoteric guar gum, obtained from Meyhall AB, Switzerland.
MEYPROID~ 9801, a cationic guar gum product having an N-content of 2%, obtained from Meyhall AG, Switzer-land.
GENDRIV~ 158, a cationic guar gum product having an N-content of 1.43%, obtained from Henkel Corpora-tion, Minneapolis, Minnesota, USA.
* trade mark ~:7~
G~NDRIV~ 162, a cationic guar gum product having an N-content of 1.71~, obtained from Henkel Corpora-tion, Minneapolis, Minnesota, USA.
Polyacrylamide products PAM I* a polyacrylamide designated XZ 87431 obtained from Dow Chemical Rheinwerk GmbH, Reinmunster, West Germany and having a cationic activity of 0.22 meq/g and an approximate molecular weight of 5 million.
PAM II* a polyacrylamide designated XZ 87409 obtained from Dow Chemical Rheinwerk GmbH, Reinmunster, West Germany and having a cationic activity of 0.50 meq/g and an approximate molecular weight of 5 million.
PAM III, a polyacrylamide designated XZ 87410 obtained from Dow Chemical Rheinwerk GmbH, ReinmUnster, West Germany and having a cationic activity of 0.83 meq/g and an approximate molecular weight of 5 million.
PAM I~, a polyacrylamide designated XZ B7407 obtained from Dow Chemical Rheinwerk GmbH, ReinmUnster, West Germany and having a cationic activity of 2.20 meq/g and an approximate molecular weight of 5 million.
Polyethylene oxide POLYOX COAGULANT* a coagulant obtained from Union Carbide Corporation, USA.
POLYOX WSR 301, a polyethylene oxide product obtained from Union Carbide Corporation, USA.
Other roducts P
BUBOND 60, a low-molecular weight product having high cationic activity and obtained from Buckman Labo-ratories, USA
* trade mark 13 ~;27~,~13 BUBOND 65, a high-molecular weight product having high cationic activity and obtained from Buckman Labora-tories, USA.
BUFLOCK 171, a low-molecular weight product having high cationic activity and obtained from Buckman Laboratories, USA.
This Example relates to a drainage test using a Canadian Freeness Tester. The paper grade used was supercalendered magazine paper. The stock comprised 76% fibre and 24% filler (C-clay from English China Clay). The fibre fraction of the stock had the following composi~ion:
22% fully bleached pine sulphate pulp 15% dithionite-bleached thermomechanical pulp 35% groundwood pulp 28% broke.
The stock was taken from a commercial magazine papermaking machine and was diluted with white water from the same machine to a stock concentration of 3 g/l. The white water had a specific conductivity of 85 mS~m and a total organic content TOC = 270 mg/l.
The pH of the stock was adjusted to 5.5 with diluted sodium hydroxide solution. For different chemical dosages, the drainability of the stock was determined according to SCAN-C 21:65 in a Canadian Freeness Tester.
As inorganic sol, use was made of a 15% Al-silicic acid sol having a surface area of about 500 m2/g and * trade mark 14 a ratio of SiO2:Na2O of about 40 and 9% Al atoms on the sol particle surface which gives 0.46% on the total solids substance of the sol.
Tes-ts were carried out with both various polymers alone and various polymers combined with 0.3% inorganic sol, calculated on dry material. In the tests, 1000 ml of stock suspension was placed in a beaker having an agitator driven at a speed of 800 rpm ("Britt-jar").
In the tests with the various polymers alone, the Eollowing sequence of steps was used:
1. Addition of drainage and retention polymer to the stock suspension under agitation.
2. Agitation for 45 sec.
3. Drainage.
In tests using a combination of polymer and sol, the following sequence of steps was used:
1. Addition of drainage and retention polymer under agitation.
2. Agitation for 30 sec.
3. Addition of inorganic sol under agitation.
In tests using a combination of polymer and sol, the following sequence of steps was used:
1. Addition of drainage and retention polymer under agitation.
2. Agitation for 30 sec.
3. Addition of inorganic sol under agitation.
4. Agitation for 15 sec.
5~ Drainage.
Table 1 and Fig. 1 show the results of chemical dosage for obtaining maximum drainability, expressed as millilitre CSF. Fig. 1 shows the considerably improved drainability when using a combination of inorganic sol and polyacrylamide (Tests 5-8), and the best prior art systems using cationic starch in combination with ~9! ;27~ IIL3 inorganic sol (Tests 18, 20, and 22-26), and a com-bination of inorganic sol and guar gum (Tests 15-17).
The detrimental effect of the trash substances dissolved from the thermomechanical pulp and groundwood pulp is manifest in these known systems as compared with the system according to the invention.
In another series of tests using the same stock, the concentration of inorganic sol was maintained constant at 0.3~, b~t the added amounts of starch, guar gum or polyacrylamide were varied. The results of these tests are given in Table 2 and illustrated in Figs. 2 and 3. As appears from Table 2 and Figs. 2 and 3, drainage was improved in the -two known processes and also in the process according to the invention.
Thus, Fig. 2 illustrates the improvements obtained with the known technique as disclosed in European patent specification EP-B-0,041,056 (Tests 28-33) and the process as disclosed in European patent speci-fication EP-B-0,080,986 (Tests 34-38). However, when using the system according to the invention (Tests 39-50), the drainability was substantially improved at lower additions of the polyacrylamide.
This Example relates to a drainage test using mechanical pulps, namely groundwood pulp, chemi-thermo-mechanical pulp (CTMP), and peroxide-bleached thermo-mechanical pulp (TMP). The same inorganic sol was used as in Example 1.
~7~ 3 Groundwood pulp (spruce) and TMP were taken from two magazine papermaking mills. By centrifugation, the two pulps were concentrated to about 30% dry solids content. The thermomechanica:L pulp was dried at room temperature to about 90% dry solids content. The chemi-thermomechanical pulp (spruce) was taken in the dry state from a pulp-mill and had a dry solids content of about 95%.
The pulps were placed for a sufficient time in deionized water and thereafter slushed in a wet-slusher (according to SCAN-M2:64). After slushing, the pulp suspensions were diluted to 0.3% (3 g/1) with deion-ized water. To the resulting stock was added 1.5 g/1 NaS04.10H20, corresponding to a specific conductivity of about 85 mS/m, such that the specific conductivity was the same as in Example 1, in which white water from a papermaking machine was used.
The pH of the stock suspension was adjusted to 4 or 8 b~7 means of diluted NaOH and H2S04 solutions.
Drainage tests according to SCAN-C 21:65 were carried out with various PAM products alone and combinations of the various PAM and sol under the same test condi-tions as in Example 1. The test results are given in Tables 3-7 and Figs. 4-8.
It clearly appears from these results that a combination of polyacrylamide and inorganic sol gives higher drainage effects that polyacrylamides used alone. The level of the technical effect depends on ~764~3 the pH of the stock, the cationic activity of the polyacrylamide, the chemical character of the pulp, and on the chemical composition of the water phase.
In all cases, the improvement obtained by the addition of polyacrylamide is manifest.
The tests accounted for in Table 7 and Fig. 8 were meant to establish the limit values for the addi-tion of the aluminium-modified silicic acid sol. The concentration of the added sol was thus varied from 0.025% to 1%. With 0.025% sol, an improvement in drain-ability of about 40-50 ml CSF was obtained as compared with the use of polyacrylamide alone. Such an effect is likely to occur also at lower values for the addi-tion of the sol, but the improvement will not become as notable. The upper limit has been studied at an addition of up to 1% (10 kg/ton of paper), but there is nothing to indicate that the effect would be lost at higher addition levels. A practical upper limit therefore is i.5% while, for practical reasons, the lower limit is 0.005% for this chemical. The same values apply to the polyacrylamide chemical.
This Example relates to a drainage test using unbleached sulphate pulp with a kappa number of 53, using a Canadian Freeness Tester according to SCAN--C
21:65. The sol used was the same as in Example l.
In this test, 360 g dry pulp was placed in 5 litre deionized water for about 20 h. The pulp was thereafter beaten accorcling to SCAN-C 25:76 to a beating degree of about 90 ml CSF. The beating time was about 75 min.
The beaten pulp was thereafter diluted with deionized water to a concentration of 3 g/l (0.3%~. 1.5 g/l Na2SO4.].0H20 was thereafter added to the fibre suspen-sion, and the pH of the fibre suspension was adjusted with diluted NaOH or H2S04 to pH 4 or 8.
The other test conditions were the same as in Examples 1 and 2 (order and time for the addition of chemicals, speed and time for agitation).
The resul.ts are given in Table 8 and also illu-strated in Figs. 9 and 10. The inventive effect clear-ly appears from these results. The effect is dependent primarily on the pH of the pulp and the chemical com-position of the water phase tsalt content and presence of dissolved organic substances).
This Example relates to a drainage test for esta-blishing ash reten-tion. The stock used had the same composition as that in Example 1. In thi.s Example, too, use was made of the same inorganic sol as in Example 1.
For the retention measurements, use was made of a so-called dynamic dewatering jar ("Britt-jar"), the first 100 ml of the filtrate was collected in a measuring glass. In the measuremen-ts, use was made of a wire having a mesh size of 76 ~m. The chemical dosage method and the agitation technique were the same as in Examples 1-3, and the total time of agita-tion after chemical dosage was 45 sec. The agitator speed was 800 rpm. The dosage of the colloidal alu-mium-modified silicic acid sol was carried out 30 sec.
after the dosage of the polyacrylamide.
The retention measurement method is described by K. Britt and J.E. Unbehend in Research Report 75, 1/10, 1981, published by Empire State Paper Research Institute ESPRA, Syracuse, N.Y. 13210, USA.
From the results in Table 9 and Fig. 11 it appears that a higher ash retention is obtained with a com-bination of polyacrylamide and aluminium-modified silicic acid sol than with polyacrylamide alone.
This Example relates to a drainage test using groundwood pulp. In the test, use was made of two types of sols, namely the same Al-silicic acid sol as in Example 1 and, as a reference, a pure silicic acid sol in the form of a 15% sol having a surface area of about 500 m2/g and a ratio of SiO2:Na2O of about 40.
The groundwood pulp (spruce) was taken from a magazine papermaking mill. By centrifugation, the pulp was concentrated to about 30~ dry solids con-tent. After the pulp had been placed for a sufficient time in deionized water, it was beaten in a wet-slusher (according to SCAN-M2:64). After slushing, the pulp suspension was diluted to 0.3~ (3 g/1) with deionized i4~3 water. To the tllus ot)-tained stock was added 1.5 g/l Na2SO4.10~-l20, corresoncling to a specific conductivity of about 85 mS/m, such that the specific conductivity was the same as in ~xample 1, in which white water from a papermaking machlne was used.
The pH value o~ the stock suspension was adjusted to 8 with a d~luted ~aOH solution. Drainage tests according to SCAN-C21:65 were carried out using PAM
alone and combinations of PAM and unmodified silicic acid sol or PAM and aluminium-modified silicic acid sol, under the same test conditions as in Example l.
The test results are given in Table 10 and Fig. 12.
It clearly appears from these results that a combination of polyacrylamide and inorganic sol gives improved drainability as compared with polyacrylamide alone and that the aluminium-modified sol gives a markedly improved result as compared with the unmo-dified pure silicic acid sol.
In addition to the above-mentioned tests, a compari-son was made between drainage tests using extremely high addition levels of polyacrylamide (PAM III) and the same inorganic sol as in Example 1, and at extreme pH
values~ These drainage tests were conducted in the man-ner described in Example 1, both on the stock suspen-sion of groundwood pulp described in Example 5 and on a chemical pulp (bleached sulphate). The results are given in Tables 11 and 12.
~ ~7~3~3 ChemLcal dosage for maximum CSF
CSF (ml) " ! C -I ¦ Cont~nt without Wi th 0.3%
- t~ sol sol ` 7~ t I - I 90 2 i JRGAN~ORE - I 1.0 ¦170 ¦ _ )R.,AN[)?rJI I O.û5 3 1 ?ûL~OY-C:~dguldnt ! 05-0.50 97 ¦~; PO!YOX-WSR 301 0.05-0.5098 S ! PAM-I 0.20 150 450 6 PAM-II 0.50 220 5g5 7 PAM-II- 0.33 280 555 8 PAM-IV 0.50 405 595 9 BUFLOC-171 0.03-0.5095 BUBONû-65 0.27 100 11 BUBOND-60 0.03-0.50100 12 POLYMIN-SK 0.33 320 155 13 POLYMIN-SN 0.50 135 160 14 MEYPROBONû-120 0.40 85 GENDRIV-158 0.4 115 277 16 GENûRIV-162 0.4 125 385 17 MEYPROBONO-9801 0.4 160 385 18 WM-International Laing 1.5 115 200 19 WAXI-MAIZE 2.0 115 200 SOLVITOSE-N 1.5 95 135 21 CATO-210 2.0 105 155 22 RAISIO-SP 190 2.0 95 155 23 HKS 0.4 110 150 24 SOLVIT05r-û9 0.5 140 230 BMB-l90 1.5 115 270 26 BMB-165 1.5 130 200 .
~L27t~413 Drainability as a function of added arnount of polymer at constant content o inorganic sol__O 3~) _ .
¦ T ~ 2 ~ P A M - I I IC S F ( m l ) ~ithout ~i th~
% _ Y. sol so i I ?7 _ _ _ j _ _ 90 i ~8 I~ 3 ~ _ 105 12 29 0 5 1 - i _ I _ lQ5 145 0.8 1 _ - _ 110 200 31 1. C I - . _ 110 250 32 1.5 , _ _ _ 115 270 33 2.0 j _ _ _ 120 245 34 _ 10.2 _ _ 130 250 _ 0.4 _ _ 125 385 36 1 _ 0.6 _ _ 110 315 37 _ 0.8 _ _ 100 240 38 _ 1.0 _ _ 90 160 39 _ _ 0.067 _ 145 165 _ _ 0.133 _ 170 260 41 _ _ 0.20 _ 180 340 42 _ _ 0.267 _ 200 425 43 _ _ 0.333 _ 220 510 44 _ _ 0.50 _ 220 595 _ _ _ 0.067 160 240 46 _ _ _ 0.133 195 305 47 _ _ _ 0.20 210 465 48 _ _ _ 0.267 240 535 49 _ _ _ 0.333 280 555 __ _ 0.50 270 550 ~L27691~L3 -_ h ` O ~ ~, C 1~ ~O O u u ~r~ ~r~ r ~ ~ r r ~ "~ `O
o -~ (\I N ~ 131 ~N I N ~ r ~ 1 ir r~
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0 21~ I I I I I O O O O' O
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h. O O O O O O O O
__ _ ~7~ L3 TABI,E ~
PEROXIDE-BLEACHED TMP PULP
CSF = 5~ sp~ci:Fic conductiviry = ~5 mS/m PAH I l :-,o l C SF P~M IV Sol CSF i X ~~ p H = 4 ) ~ ,~6 ~ p H - 8) _ - 6~ _ - S7 . C~, - 6~ 0.05 - 67 0. ' ~' - 63 0.10 - 93 0. /3 - 73 0.20 - 202 .30 - 31 0.30 - 455 ~'.5n - a6 0. S0 - 532 ~`.3~ 0.3 72 0.050.367 G .1()3.3 81 0.100.391 0.~0 0.3 135 0.200.3230 0.30 0.3 237 0.300.3490 0.50 0.3 492 ~ 0.500.3600 L
CTMP pulp CSF = 106, specific conductivity 85 mS/m PAM I I Sol CSF PAM IV Sol CSF
% %( pH -4) % %( p H; 8) 0.05 - 145 0.05 - 177 0.10 - 155 0.10 - 295 0.20 - 170 0.20 - 490 0.30 - 180 0.30 - 565 0.50 - 203 0.50 - 595 0.05 0.3 182 05 0.3206 0.10 0.3 265 0.100.3295 0.20 0.3 472 0.200.3545 0.30 0.3 607 0-30 0.3615 0.50 0.3 670 L 50 0.3605 , , C ~ I L~ O ~ =I L^~ J~ O U--\ O U`l O
~ CO
~ O _ ~ _ O L O U~
~ ~
_ I L~I
_ O O O O O
Z ~ ~ U~ oo o o U~ o o o o ~1 ~ ~ ~ o o o o o o o o o o m ¦ ~ O _ __ _ _ 3 Lr~ co ~ o ou~ u~ O u~ Lf\ .r~ Lr~ u~
E~ 11 ~ ~ ~o 1- 1- CO ~ o~
1~ 1~1 U ) I
E-~ 1~ ~
E~ O L. Il O Lt\u~ U~ O O L~ O O
~Ll O Ul I ~ ~ U~ l C0 1` ~ ~0 ~
H a .. ~ _ _ _ ~ N
~ o ~e ~ o o o o o ~ U~ O O O O U~ O O O O
C~ _ o _ c~ o 1_~ ~
~ E O O O O O O O O O O
~276qL~;3 I L. o ~ o o o I ~. , , ~
I
o o o o o o _ ~ ; . _ ! " j '~ O O O
l _ I
_, 0 3 0 ~ O
~ b ' ' b o - o L. u~ O O '~
h I I ~I N 0 0 1 0 _ O O O O O O
~1 o o u~ o U~ I I -- 1-- N 0 _ _~ O O O O O
O ~R O I O O O O
I~0 o o~ a I I
~ U~
_ NN o o o ~ ~ O O O O O
_ L. O O O Lr~ U~
(_) 0~ O I I I I I I I
O N I \ U~
C~ O O O O O O O
4~3 I ~ r PAM II Sol CSF
(pH=4) % o ( pH=~3) 265 _ _ _ _ __ 200 ! o.lo ~370 0.10 _ 360 0.25 - I465 0.20 _ 435 0.30 1 - I 480 0.30 _ 475 0.40 ~ 505 0.40 _ 530 0.~0 ~ 30 0.50 _ 560 I 0.09 0.3 1375 O.lo 0.3 340 1 0.25 i 0.3 1570 0.20 0.3 485 0.30 ~ 0.3 610 0.30 0.3 610 0.40 0.3 660 0.40 0.3 660 0.50 L _ 695 l 0 50 0 3 685 __ PAM I Ash retention %, pH-4 Ash reten-tion%, pH=5.5 % withoutwith 0.3% without with 0.3%
sol sol sol sol _ _ .
O 11 _ 6 0.1 65 77.5 75.5 7 0.2 85 96.5 90.5 98 0.3 94 95 95 ,~7 _ _ _ ~:7~
¦ PA~I lt 1 SiO2 ~ol ¦ Al~modif1ed CSF
SiO2 sol(ml) t_~ -~ - 1 40 o.o, . - I _ 65 O . 10 -- - 65 0./0 - ~ 70 0.~0 1 - ~ - ~ 75 0.40 ' - I - I _ O . 50 1 - _ 1 75 0.05 1 0.3 _ 55 I 0.10 ' 0.3 _ 70 j 0.20 ll 0.3 _ 65 0.30 0'3 _ 22' 0.05 _ 0.3 55 0.10 _ 0.3 65 0.20 _ 0.3 105 0.30 _ 0.3 170 0.4 _ 0.3 270 0.5 1 0.3 1400 Groundwood pulp (100%) pH = 4Ø Specific conductivity = 85 mS/
PAM III Al-modified CSF
sio2 sol % ~____ ml .
_ _ 40-50 1.0 1.0 470 1.0 1.5 700 1.5 1.5 610 ~7~ 3 Chemical r~ul~00^~) ~cific conductivi-ty = 85 mS/m -----r-- ~ I pH
Sio2 sol ~ -T~ _ 0.2 1 0.3 1 545 3.0 (.2 1 0.3 550 10 3û
Table 1 and Fig. 1 show the results of chemical dosage for obtaining maximum drainability, expressed as millilitre CSF. Fig. 1 shows the considerably improved drainability when using a combination of inorganic sol and polyacrylamide (Tests 5-8), and the best prior art systems using cationic starch in combination with ~9! ;27~ IIL3 inorganic sol (Tests 18, 20, and 22-26), and a com-bination of inorganic sol and guar gum (Tests 15-17).
The detrimental effect of the trash substances dissolved from the thermomechanical pulp and groundwood pulp is manifest in these known systems as compared with the system according to the invention.
In another series of tests using the same stock, the concentration of inorganic sol was maintained constant at 0.3~, b~t the added amounts of starch, guar gum or polyacrylamide were varied. The results of these tests are given in Table 2 and illustrated in Figs. 2 and 3. As appears from Table 2 and Figs. 2 and 3, drainage was improved in the -two known processes and also in the process according to the invention.
Thus, Fig. 2 illustrates the improvements obtained with the known technique as disclosed in European patent specification EP-B-0,041,056 (Tests 28-33) and the process as disclosed in European patent speci-fication EP-B-0,080,986 (Tests 34-38). However, when using the system according to the invention (Tests 39-50), the drainability was substantially improved at lower additions of the polyacrylamide.
This Example relates to a drainage test using mechanical pulps, namely groundwood pulp, chemi-thermo-mechanical pulp (CTMP), and peroxide-bleached thermo-mechanical pulp (TMP). The same inorganic sol was used as in Example 1.
~7~ 3 Groundwood pulp (spruce) and TMP were taken from two magazine papermaking mills. By centrifugation, the two pulps were concentrated to about 30% dry solids content. The thermomechanica:L pulp was dried at room temperature to about 90% dry solids content. The chemi-thermomechanical pulp (spruce) was taken in the dry state from a pulp-mill and had a dry solids content of about 95%.
The pulps were placed for a sufficient time in deionized water and thereafter slushed in a wet-slusher (according to SCAN-M2:64). After slushing, the pulp suspensions were diluted to 0.3% (3 g/1) with deion-ized water. To the resulting stock was added 1.5 g/1 NaS04.10H20, corresponding to a specific conductivity of about 85 mS/m, such that the specific conductivity was the same as in Example 1, in which white water from a papermaking machine was used.
The pH of the stock suspension was adjusted to 4 or 8 b~7 means of diluted NaOH and H2S04 solutions.
Drainage tests according to SCAN-C 21:65 were carried out with various PAM products alone and combinations of the various PAM and sol under the same test condi-tions as in Example 1. The test results are given in Tables 3-7 and Figs. 4-8.
It clearly appears from these results that a combination of polyacrylamide and inorganic sol gives higher drainage effects that polyacrylamides used alone. The level of the technical effect depends on ~764~3 the pH of the stock, the cationic activity of the polyacrylamide, the chemical character of the pulp, and on the chemical composition of the water phase.
In all cases, the improvement obtained by the addition of polyacrylamide is manifest.
The tests accounted for in Table 7 and Fig. 8 were meant to establish the limit values for the addi-tion of the aluminium-modified silicic acid sol. The concentration of the added sol was thus varied from 0.025% to 1%. With 0.025% sol, an improvement in drain-ability of about 40-50 ml CSF was obtained as compared with the use of polyacrylamide alone. Such an effect is likely to occur also at lower values for the addi-tion of the sol, but the improvement will not become as notable. The upper limit has been studied at an addition of up to 1% (10 kg/ton of paper), but there is nothing to indicate that the effect would be lost at higher addition levels. A practical upper limit therefore is i.5% while, for practical reasons, the lower limit is 0.005% for this chemical. The same values apply to the polyacrylamide chemical.
This Example relates to a drainage test using unbleached sulphate pulp with a kappa number of 53, using a Canadian Freeness Tester according to SCAN--C
21:65. The sol used was the same as in Example l.
In this test, 360 g dry pulp was placed in 5 litre deionized water for about 20 h. The pulp was thereafter beaten accorcling to SCAN-C 25:76 to a beating degree of about 90 ml CSF. The beating time was about 75 min.
The beaten pulp was thereafter diluted with deionized water to a concentration of 3 g/l (0.3%~. 1.5 g/l Na2SO4.].0H20 was thereafter added to the fibre suspen-sion, and the pH of the fibre suspension was adjusted with diluted NaOH or H2S04 to pH 4 or 8.
The other test conditions were the same as in Examples 1 and 2 (order and time for the addition of chemicals, speed and time for agitation).
The resul.ts are given in Table 8 and also illu-strated in Figs. 9 and 10. The inventive effect clear-ly appears from these results. The effect is dependent primarily on the pH of the pulp and the chemical com-position of the water phase tsalt content and presence of dissolved organic substances).
This Example relates to a drainage test for esta-blishing ash reten-tion. The stock used had the same composition as that in Example 1. In thi.s Example, too, use was made of the same inorganic sol as in Example 1.
For the retention measurements, use was made of a so-called dynamic dewatering jar ("Britt-jar"), the first 100 ml of the filtrate was collected in a measuring glass. In the measuremen-ts, use was made of a wire having a mesh size of 76 ~m. The chemical dosage method and the agitation technique were the same as in Examples 1-3, and the total time of agita-tion after chemical dosage was 45 sec. The agitator speed was 800 rpm. The dosage of the colloidal alu-mium-modified silicic acid sol was carried out 30 sec.
after the dosage of the polyacrylamide.
The retention measurement method is described by K. Britt and J.E. Unbehend in Research Report 75, 1/10, 1981, published by Empire State Paper Research Institute ESPRA, Syracuse, N.Y. 13210, USA.
From the results in Table 9 and Fig. 11 it appears that a higher ash retention is obtained with a com-bination of polyacrylamide and aluminium-modified silicic acid sol than with polyacrylamide alone.
This Example relates to a drainage test using groundwood pulp. In the test, use was made of two types of sols, namely the same Al-silicic acid sol as in Example 1 and, as a reference, a pure silicic acid sol in the form of a 15% sol having a surface area of about 500 m2/g and a ratio of SiO2:Na2O of about 40.
The groundwood pulp (spruce) was taken from a magazine papermaking mill. By centrifugation, the pulp was concentrated to about 30~ dry solids con-tent. After the pulp had been placed for a sufficient time in deionized water, it was beaten in a wet-slusher (according to SCAN-M2:64). After slushing, the pulp suspension was diluted to 0.3~ (3 g/1) with deionized i4~3 water. To the tllus ot)-tained stock was added 1.5 g/l Na2SO4.10~-l20, corresoncling to a specific conductivity of about 85 mS/m, such that the specific conductivity was the same as in ~xample 1, in which white water from a papermaking machlne was used.
The pH value o~ the stock suspension was adjusted to 8 with a d~luted ~aOH solution. Drainage tests according to SCAN-C21:65 were carried out using PAM
alone and combinations of PAM and unmodified silicic acid sol or PAM and aluminium-modified silicic acid sol, under the same test conditions as in Example l.
The test results are given in Table 10 and Fig. 12.
It clearly appears from these results that a combination of polyacrylamide and inorganic sol gives improved drainability as compared with polyacrylamide alone and that the aluminium-modified sol gives a markedly improved result as compared with the unmo-dified pure silicic acid sol.
In addition to the above-mentioned tests, a compari-son was made between drainage tests using extremely high addition levels of polyacrylamide (PAM III) and the same inorganic sol as in Example 1, and at extreme pH
values~ These drainage tests were conducted in the man-ner described in Example 1, both on the stock suspen-sion of groundwood pulp described in Example 5 and on a chemical pulp (bleached sulphate). The results are given in Tables 11 and 12.
~ ~7~3~3 ChemLcal dosage for maximum CSF
CSF (ml) " ! C -I ¦ Cont~nt without Wi th 0.3%
- t~ sol sol ` 7~ t I - I 90 2 i JRGAN~ORE - I 1.0 ¦170 ¦ _ )R.,AN[)?rJI I O.û5 3 1 ?ûL~OY-C:~dguldnt ! 05-0.50 97 ¦~; PO!YOX-WSR 301 0.05-0.5098 S ! PAM-I 0.20 150 450 6 PAM-II 0.50 220 5g5 7 PAM-II- 0.33 280 555 8 PAM-IV 0.50 405 595 9 BUFLOC-171 0.03-0.5095 BUBONû-65 0.27 100 11 BUBOND-60 0.03-0.50100 12 POLYMIN-SK 0.33 320 155 13 POLYMIN-SN 0.50 135 160 14 MEYPROBONû-120 0.40 85 GENDRIV-158 0.4 115 277 16 GENûRIV-162 0.4 125 385 17 MEYPROBONO-9801 0.4 160 385 18 WM-International Laing 1.5 115 200 19 WAXI-MAIZE 2.0 115 200 SOLVITOSE-N 1.5 95 135 21 CATO-210 2.0 105 155 22 RAISIO-SP 190 2.0 95 155 23 HKS 0.4 110 150 24 SOLVIT05r-û9 0.5 140 230 BMB-l90 1.5 115 270 26 BMB-165 1.5 130 200 .
~L27t~413 Drainability as a function of added arnount of polymer at constant content o inorganic sol__O 3~) _ .
¦ T ~ 2 ~ P A M - I I IC S F ( m l ) ~ithout ~i th~
% _ Y. sol so i I ?7 _ _ _ j _ _ 90 i ~8 I~ 3 ~ _ 105 12 29 0 5 1 - i _ I _ lQ5 145 0.8 1 _ - _ 110 200 31 1. C I - . _ 110 250 32 1.5 , _ _ _ 115 270 33 2.0 j _ _ _ 120 245 34 _ 10.2 _ _ 130 250 _ 0.4 _ _ 125 385 36 1 _ 0.6 _ _ 110 315 37 _ 0.8 _ _ 100 240 38 _ 1.0 _ _ 90 160 39 _ _ 0.067 _ 145 165 _ _ 0.133 _ 170 260 41 _ _ 0.20 _ 180 340 42 _ _ 0.267 _ 200 425 43 _ _ 0.333 _ 220 510 44 _ _ 0.50 _ 220 595 _ _ _ 0.067 160 240 46 _ _ _ 0.133 195 305 47 _ _ _ 0.20 210 465 48 _ _ _ 0.267 240 535 49 _ _ _ 0.333 280 555 __ _ 0.50 270 550 ~L27691~L3 -_ h ` O ~ ~, C 1~ ~O O u u ~r~ ~r~ r ~ ~ r r ~ "~ `O
o -~ (\I N ~ 131 ~N I N ~ r ~ 1 ir r~
! 2~D - ~ O O O O O
~
_~ ~'~ _~ U~
;I ~ '~ N ~ 0 0 0 I ~; ._, I O O ~ O O ~ ~
h ~___ O '-- O O O O O O O O
U O U ~ ` O U~ U o o ! ~ ~ - ~ ~ ~ ir ~ ) _~
,- ~ O O O ~ U~ ~ U
_ I l ~ ~ N N N N -- ~ u~ ~0 O
J~ ~_ r~ I O O O
2~ ~ U-\
Z s-3~ I o _ N r~ u~ N l~o N r~
I h. O O O O O O O O O O
[~1 I~I
m ~ o O ~ u~ O ,~
~:I U (~ I~\ ~ N ~ O -- ~
E~
H h I I U~ r~ ~ u~ 0 o U'\ ~o 0 N
F~ r~ r~ r~ r~ r-~
~Ll O _~ I ~ I I 1 00'000 1 Z o e N 1'~ ~ O _I N
O h 11 U~ O O 1~ 0 0 0 0 Ir\
3 Vl I irir ir r~ r'`l O r~) O r'`l I
O _~
h-- 1~ r Ir~ N O u~ O O r~ o U~ C~
C_) I irir ir ir ~r _ N N N --r~ r~ r~\ r~
0 21~ I I I I I O O O O' O
S ~ I _ N r~ ~I N r~ ~ O
h. O O O O O O O O
__ _ ~7~ L3 TABI,E ~
PEROXIDE-BLEACHED TMP PULP
CSF = 5~ sp~ci:Fic conductiviry = ~5 mS/m PAH I l :-,o l C SF P~M IV Sol CSF i X ~~ p H = 4 ) ~ ,~6 ~ p H - 8) _ - 6~ _ - S7 . C~, - 6~ 0.05 - 67 0. ' ~' - 63 0.10 - 93 0. /3 - 73 0.20 - 202 .30 - 31 0.30 - 455 ~'.5n - a6 0. S0 - 532 ~`.3~ 0.3 72 0.050.367 G .1()3.3 81 0.100.391 0.~0 0.3 135 0.200.3230 0.30 0.3 237 0.300.3490 0.50 0.3 492 ~ 0.500.3600 L
CTMP pulp CSF = 106, specific conductivity 85 mS/m PAM I I Sol CSF PAM IV Sol CSF
% %( pH -4) % %( p H; 8) 0.05 - 145 0.05 - 177 0.10 - 155 0.10 - 295 0.20 - 170 0.20 - 490 0.30 - 180 0.30 - 565 0.50 - 203 0.50 - 595 0.05 0.3 182 05 0.3206 0.10 0.3 265 0.100.3295 0.20 0.3 472 0.200.3545 0.30 0.3 607 0-30 0.3615 0.50 0.3 670 L 50 0.3605 , , C ~ I L~ O ~ =I L^~ J~ O U--\ O U`l O
~ CO
~ O _ ~ _ O L O U~
~ ~
_ I L~I
_ O O O O O
Z ~ ~ U~ oo o o U~ o o o o ~1 ~ ~ ~ o o o o o o o o o o m ¦ ~ O _ __ _ _ 3 Lr~ co ~ o ou~ u~ O u~ Lf\ .r~ Lr~ u~
E~ 11 ~ ~ ~o 1- 1- CO ~ o~
1~ 1~1 U ) I
E-~ 1~ ~
E~ O L. Il O Lt\u~ U~ O O L~ O O
~Ll O Ul I ~ ~ U~ l C0 1` ~ ~0 ~
H a .. ~ _ _ _ ~ N
~ o ~e ~ o o o o o ~ U~ O O O O U~ O O O O
C~ _ o _ c~ o 1_~ ~
~ E O O O O O O O O O O
~276qL~;3 I L. o ~ o o o I ~. , , ~
I
o o o o o o _ ~ ; . _ ! " j '~ O O O
l _ I
_, 0 3 0 ~ O
~ b ' ' b o - o L. u~ O O '~
h I I ~I N 0 0 1 0 _ O O O O O O
~1 o o u~ o U~ I I -- 1-- N 0 _ _~ O O O O O
O ~R O I O O O O
I~0 o o~ a I I
~ U~
_ NN o o o ~ ~ O O O O O
_ L. O O O Lr~ U~
(_) 0~ O I I I I I I I
O N I \ U~
C~ O O O O O O O
4~3 I ~ r PAM II Sol CSF
(pH=4) % o ( pH=~3) 265 _ _ _ _ __ 200 ! o.lo ~370 0.10 _ 360 0.25 - I465 0.20 _ 435 0.30 1 - I 480 0.30 _ 475 0.40 ~ 505 0.40 _ 530 0.~0 ~ 30 0.50 _ 560 I 0.09 0.3 1375 O.lo 0.3 340 1 0.25 i 0.3 1570 0.20 0.3 485 0.30 ~ 0.3 610 0.30 0.3 610 0.40 0.3 660 0.40 0.3 660 0.50 L _ 695 l 0 50 0 3 685 __ PAM I Ash retention %, pH-4 Ash reten-tion%, pH=5.5 % withoutwith 0.3% without with 0.3%
sol sol sol sol _ _ .
O 11 _ 6 0.1 65 77.5 75.5 7 0.2 85 96.5 90.5 98 0.3 94 95 95 ,~7 _ _ _ ~:7~
¦ PA~I lt 1 SiO2 ~ol ¦ Al~modif1ed CSF
SiO2 sol(ml) t_~ -~ - 1 40 o.o, . - I _ 65 O . 10 -- - 65 0./0 - ~ 70 0.~0 1 - ~ - ~ 75 0.40 ' - I - I _ O . 50 1 - _ 1 75 0.05 1 0.3 _ 55 I 0.10 ' 0.3 _ 70 j 0.20 ll 0.3 _ 65 0.30 0'3 _ 22' 0.05 _ 0.3 55 0.10 _ 0.3 65 0.20 _ 0.3 105 0.30 _ 0.3 170 0.4 _ 0.3 270 0.5 1 0.3 1400 Groundwood pulp (100%) pH = 4Ø Specific conductivity = 85 mS/
PAM III Al-modified CSF
sio2 sol % ~____ ml .
_ _ 40-50 1.0 1.0 470 1.0 1.5 700 1.5 1.5 610 ~7~ 3 Chemical r~ul~00^~) ~cific conductivi-ty = 85 mS/m -----r-- ~ I pH
Sio2 sol ~ -T~ _ 0.2 1 0.3 1 545 3.0 (.2 1 0.3 550 10 3û
Claims (14)
1. A papermaking process in which an aqueous paper pulp containing cellulosic pulp and, optionally, also mineral filler, is formed and dried, drainage- and retention-improving chemicals being added to the paper pulp prior to forming, characterized in that the drainage- and retention-improving chemicals added are a cationic polyacrylamide and a sol of colloidal particles having at least one surface layer of aluminium silicate or aluminium-modified silicic acid, such that the surface groups of the particles contain silicon atoms and aluminium atoms in a ratio of from 9.5:0.5 to 7.5:2.5.
2. Method as claimed in claim 1, characterized in that the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock.
3. Process as claimed in claim 1, characterized in that the sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock.
4. Process as claimed in claim 1, characterized in that the sole has sol particles of a surface area of from about 50 to about 1000 m2/g, preferably from about 300 to about 700 m2/g.
5. Process as claimed in claim 1, characterized in that the pH of the paper pulp is adjusted to from about 3.5 to about 10.
6. Process as claimed in claim 1, characterized in that the amount of cellulosic pulp in the paper pulp is adjusted to give a finished paper having a least 50% by weight of cellulosic fibres.
7. The process of claim 3, characterized in that the cationic polyacrylamide is added in an amount of 0.005-1.5%
by weight, calculated on dry paper stock.
by weight, calculated on dry paper stock.
8. The process of claim 4, further comprising one or both of the following features:
(a) the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock; and (b) sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock.
(a) the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock; and (b) sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock.
9. The process of claim 5, further comprising one or more of the following features:
(a) the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock;
(b) sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock; and (c) the sol has sol particles of a surface area of from about 50 to about 1000 m2/g, preferably from about 300 to about 700 m2/g.
(a) the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock;
(b) sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock; and (c) the sol has sol particles of a surface area of from about 50 to about 1000 m2/g, preferably from about 300 to about 700 m2/g.
10. The process of claim 6, further comprising one or more of the following features:
(a) the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock;
(b) sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock;
(c) the sol has sol particles of a surface area of from about 50 to about 1000 m2/g, preferably from about 300 to about 700 m2/g; and (d) the pH of the paper pulp is adjusted to from about 3.5 to about 10.
(a) the cationic polyacrylamide is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock;
(b) sol is added in an amount of 0.005-1.5% by weight, calculated on dry paper stock;
(c) the sol has sol particles of a surface area of from about 50 to about 1000 m2/g, preferably from about 300 to about 700 m2/g; and (d) the pH of the paper pulp is adjusted to from about 3.5 to about 10.
11. A paper product containing cellulosic fibres, preferably in an amount of at least 50% by weight, calculated on the paper product, and drainage- and retention-improving chemicals and, optionally, also containing mineral filler, characterized in that the drainage- and retention-improving chemicals comprise a cationic polyacrylamide, colloidal inorga-nic particles having at least one surface layer of aluminium silicate or aluminium-modified silicic acid, such that the surface groups of the particles contain silicon atoms and aluminium atoms in a ratio of from 9.5:0.5 to 7.5:2.5.
12. Paper product as claimed in claim 11, characterized in that its content of cationic polyacrylamide and its content of colloidal inorganic particles each is 0.005-1.5% by weight, calculated on the dry solids content of the paper.
13. Process as claimed in claim 1, characterized in that the sol has sol particles of a size or less than 20 microns.
14. The process of claim 13, characterized in that the particles consist of aluminum-modified silicic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8501652-5 | 1985-04-03 | ||
| SE8501652A SE451739B (en) | 1985-04-03 | 1985-04-03 | PAPER MANUFACTURING PROCEDURE AND PAPER PRODUCT WHICH DRAINAGE AND RETENTION-IMPROVING CHEMICALS USED COTTONIC POLYACRYLAMIDE AND SPECIAL INORGANIC COLLOID |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1276413C true CA1276413C (en) | 1990-11-20 |
Family
ID=20359755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000505607A Expired - Lifetime CA1276413C (en) | 1985-04-03 | 1986-04-02 | Papermaking process |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4980025A (en) |
| EP (1) | EP0218674B1 (en) |
| JP (1) | JPS63500190A (en) |
| CN (1) | CN1003799B (en) |
| AT (1) | ATE40841T1 (en) |
| AU (1) | AU579729B2 (en) |
| BR (1) | BR8607094A (en) |
| CA (1) | CA1276413C (en) |
| DE (2) | DE3662113D1 (en) |
| FI (1) | FI87672C (en) |
| NO (1) | NO166958C (en) |
| NZ (1) | NZ215658A (en) |
| RU (1) | RU2023783C1 (en) |
| SE (1) | SE451739B (en) |
| WO (1) | WO1986005826A1 (en) |
| ZA (1) | ZA862475B (en) |
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| CN102154938A (en) * | 2011-05-04 | 2011-08-17 | 南京林业大学 | Polyethylene oxide-silica sol dual-retention drainage system |
| US8721896B2 (en) | 2012-01-25 | 2014-05-13 | Sortwell & Co. | Method for dispersing and aggregating components of mineral slurries and low molecular weight multivalent polymers for mineral aggregation |
| EP3036192B1 (en) | 2013-08-23 | 2018-10-03 | Akzo Nobel Chemicals International B.V. | Silica sol |
| CN108130801B (en) | 2013-12-18 | 2020-11-24 | 艺康美国股份有限公司 | Method for producing activated colloidal silica for use in papermaking |
| CN109518521A (en) * | 2018-12-25 | 2019-03-26 | 昆山裕锦环保包装有限公司 | It is a kind of for packaging products of paper mould scrap-falling-proof processing slurry in auxiliary agent |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4309247A (en) * | 1976-03-15 | 1982-01-05 | Amf Incorporated | Filter and method of making same |
| SE419236B (en) * | 1979-06-01 | 1981-07-20 | Eka Ab | SURFACE MODIFIED PIGMENT OF NATURAL KAOLIN MATERIAL, AND FOR ITS MANUFACTURING |
| SE432951B (en) * | 1980-05-28 | 1984-04-30 | Eka Ab | PAPER PRODUCT CONTAINING CELLULOSA FIBERS AND A BINDING SYSTEM CONTAINING COLOIDAL MILIC ACID AND COTIONIC STARCH AND PROCEDURE FOR PREPARING THE PAPER PRODUCT |
| FI67736B (en) * | 1981-04-10 | 1985-01-31 | Kasvioeljy Vaextolje Oy Ab | AEMNESKOMPOSITION FOER LIMNING AV PAPPER |
| FI67735B (en) * | 1981-09-16 | 1985-01-31 | Kasvioeljy Vaextolje Oy Ab | FOERFARANDE FOER LIMNING AV PAPPER ELLER LIKNANDE PRODUKT |
| SE8107078L (en) * | 1981-11-27 | 1983-05-28 | Eka Ab | PAPER MANUFACTURING PROCEDURE |
| US4578150A (en) * | 1982-07-23 | 1986-03-25 | Amf Inc. | Fibrous media containing millimicron-sized particulates |
| SE8403062L (en) * | 1984-06-07 | 1985-12-08 | Eka Ab | PAPER MANUFACTURING PROCEDURES |
-
1985
- 1985-04-03 SE SE8501652A patent/SE451739B/en not_active IP Right Cessation
-
1986
- 1986-03-31 CN CN86102961.5A patent/CN1003799B/en not_active Expired
- 1986-04-02 AT AT86902560T patent/ATE40841T1/en not_active IP Right Cessation
- 1986-04-02 AU AU56960/86A patent/AU579729B2/en not_active Expired
- 1986-04-02 DE DE8686902560T patent/DE3662113D1/en not_active Expired
- 1986-04-02 JP JP61502255A patent/JPS63500190A/en active Granted
- 1986-04-02 DE DE198686902560T patent/DE218674T1/en active Pending
- 1986-04-02 CA CA000505607A patent/CA1276413C/en not_active Expired - Lifetime
- 1986-04-02 BR BR8607094A patent/BR8607094A/en not_active IP Right Cessation
- 1986-04-02 EP EP86902560A patent/EP0218674B1/en not_active Expired
- 1986-04-02 NZ NZ215658A patent/NZ215658A/en unknown
- 1986-04-02 WO PCT/SE1986/000152 patent/WO1986005826A1/en active IP Right Grant
- 1986-04-03 ZA ZA862475A patent/ZA862475B/en unknown
- 1986-12-02 NO NO864847A patent/NO166958C/en unknown
-
1987
- 1987-09-30 FI FI874295A patent/FI87672C/en not_active IP Right Cessation
- 1987-10-02 RU SU874203473A patent/RU2023783C1/en active
-
1989
- 1989-07-17 US US07/380,737 patent/US4980025A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63500190A (en) | 1988-01-21 |
| ZA862475B (en) | 1986-12-30 |
| RU2023783C1 (en) | 1994-11-30 |
| FI87672B (en) | 1992-10-30 |
| WO1986005826A1 (en) | 1986-10-09 |
| FI87672C (en) | 1993-02-10 |
| NO166958C (en) | 1991-09-18 |
| ATE40841T1 (en) | 1989-03-15 |
| SE8501652L (en) | 1986-10-04 |
| AU579729B2 (en) | 1988-12-08 |
| CN1003799B (en) | 1989-04-05 |
| BR8607094A (en) | 1988-01-19 |
| EP0218674A1 (en) | 1987-04-22 |
| FI874295A0 (en) | 1987-09-30 |
| NO864847L (en) | 1986-12-02 |
| US4980025A (en) | 1990-12-25 |
| SE451739B (en) | 1987-10-26 |
| CN86102961A (en) | 1986-12-17 |
| NO864847D0 (en) | 1986-12-02 |
| FI874295A (en) | 1987-09-30 |
| DE218674T1 (en) | 1987-08-13 |
| NO166958B (en) | 1991-06-10 |
| EP0218674B1 (en) | 1989-02-15 |
| SE8501652D0 (en) | 1985-04-03 |
| NZ215658A (en) | 1988-08-30 |
| JPH0327676B2 (en) | 1991-04-16 |
| AU5696086A (en) | 1986-10-23 |
| DE3662113D1 (en) | 1989-03-23 |
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