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
  • D21H17/20—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
• • 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
  • D21H17/63—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
  • 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

Definitions

• a process for the production of paper The present invention relates to a process for the production of paper utilizing an improved retention- and dewatering system. More particularly the invention relates to the use of a combination of a cationic polyacrylamide, a cationic starch and polymeric silicic acid as retention- and dewatering system in the production of paper.
• the commercial silica based colloids which have been increasingly used in papermaking together with cat ⁇ ionic polymeric retention agents during the last few years are of the type which has colloidal particles generally with a particle size of from about 4 nm to about 7 nm, ie a specific surface area of from about 700 to about 300 m 2 /g, although it is known, eg from the European patent 41056, to use polymeric silicic acid in papermaking. It has generally been considered that colloidal silicic acid sols with particles of above given size give the best results and these have also been preferred with regard to stability. In the Japanese patent application with Early-Disclosure No.
• colloidal silica with both cationic starch and a cationic or am- photeric polyacrylamide.
• the colloidal silicic acid should preferably have a surface area of from 300 to 700 m 2 /g and in all examples a colloid- al silica with a specific surface area of 500 or 550 rrr/g has been used.
• the effect of systems comprising an anionic inorganic silica based sol and a cationic component is based on interaction between two substances of different charges and it is supposed that the sol particles with their strong anionic charges to some extent give rise to cross-linking of the polymeric retention agent.
• a combination of polymeric silicic acid with two cationic polymers, cationic starch and cationic polyacryl ⁇ amide gives a surprisingly great improvement of "the retention- and dewatering effect at papermaking.
• This improvement in effect does not originate from the combina ⁇ tion of the cationic polymers as such, nor can it be predicted from the effect of the combination of the poly ⁇ meric silicic acid with the individual cationic polymers.
• a synergistic effect is obtained when cationic starch and cationic polyacrylamide are used together with the poly ⁇ meric silicic acid, as is evident from the examples. Thanks to the improved retention and dewatering a greater part of the fine fibers and optional filler is retained in the paper and at the same time the speed of the paper machine can be increased and the energy consumption in the press- and drying sections can be decreased.
• the present invention thus relates to a process for the production of paper by forming and dewatering a suspen ⁇ sion of cellulose fibers and optional fillers on a wire as stated in the appended claims.
• the polymeric silicic acid is such which is disclosed in the Swedish patent application 8801951-8, which is hereby incorporated herein by - reference.
• the polymeric silicic acid has a very high specific surface area which at its lowest is 1050 m 2 /g.
• the particles suitably have a specific surface area within the range of from 1100 to 1700 m /g and preferably within the range of from 1200 to 1600 m 2 /g.
• the given specific surface area is measured by titration according to the method disclosed by Sears in Analytical Chemistry 28(1956)1981.
• the polymeric silicic acid can be prepared by acidification of alkali metal silicate, such as potassium or sodium water glass, prefer ⁇ ably sodium water glass.
• any such alkali metal silicate or water glass can be used for the preparation of the fine particle polymeric silicic acids and this preparation is carried out by acidification of a diluted aqueous solution of the sili ⁇ cate.
• acidification mineral acids such as sul ⁇ phuric acid, hydrochloric acid and phosphoric acid, or acid ion exchange resins can for example be used.
• a number of other chemicals for acidification at production of polysilicic acid are also known and some examples of such other chemicals are ammonium sulphate and carbon dioxide.
• the acidification is carried out to a pH within the range of from 1 to 9 and suitably to a pH within the range of from 1.5 to 4.
• the polymeric silicic acid which is termed activated silicic acid, which is prepared by partial neutralization of the alkali metal content to a pH of about 8 to 9 and polymerization usually during about half an hour to an hour, can be used as such directly thereafter but must otherwise be diluted to a content of not more than 1 per cent by weight for inter ⁇ rupting the polymerization or be acidified to the preferred pH range in order to avoid gelation.
• the acidification according to the above is most suitably carried out by means of acid ion exchangers, among other things to get more stable products and to avoid that salts from the acidification are added to the stock through the polymeric silicic acid.
• the polymeric silicic acid which is formed at the acidification consists of macro- molecules or particles of a size of the order of 1 nm which form voluminous chains and networks. Compared with the silica sols of larger particle size which are used commer- cially in papermaking those which are utilized according to the present invention are considerably less stable both with regard to stability in relation to concentration and stability at storage.
• the polymeric silicic acids should thus after the acidification suitably not be present in higher concentrations than about 5 per cent by weight, and preferably not higher than 2 per cent by weight. They should not be stored for too long times but it has, nonetheless, been found that a certain storage time can be advantageous. Thus, for example, a storage of a day or a couple of days at a concentration of not more than about 4 to 5 per cent by weight is entirely acceptable with regard to stability and can even result in an improved effect. At a concentration of 1%, or below, storage for two to three weeks without impaired stability is possible and all the time with good effect, or even better effect than without " storage. After storage for about three weeks at room temperature an initial gelation is noticeable.
• polymeric silicic acids with high specific surface area by acidification as above described is the preferred method, it is also possible to prepare such polymeric silicic acids which have the high specific surface area and which consist of macromolecules or particles of a size of the order of 1 nm which form voluminous chains and networks by other methods.
• Such polymeric silicic acids can thus be prepared by polymeriza ⁇ tion of an alkali metal silicate solution using an in ⁇ itiator such as alum, sodium aluminate and sodium borate.
• the polymeric silicic acids which are used according to the present process should thus be produced in connec ⁇ tion with their use and such a production at the location in or close to a paper mill is per se advantageous in that cheap raw materials and simple preparation processes are used. The economy of the present process will thus be very good since the polymeric silicic acid is economically advantageous.
• Cationic polyacrylamides are per se known as addi ⁇ tives in papermaking, primarily to increase retention of fine fibers and fillers, and any cationic polyacrylamide can be used in the present process.
• the cationic starch can be a for papermaking conventional cationic starch.
• the starch is made cationic bv substitution with ammonium groups in a per se known manner. It is suitable to use a starch with a degree of substitution of at least 0.01.
• the amount of polymeric silicic acid which is used depends on the specific stock, the presence of fillers and other conditions at the papermaking. Too small amounts do not give any effect and too great amounts do not give any further improvement of dewatering and retention but only increased costs.
• the amount of polymeric silicic acid should suitably be at least 0.01 kg/ton, calculated as Si ⁇ 2 on dry fibers and optional fillers, and is suitably within the range from 0.05 to 5 kg/ton. Amounts within the range of from 0.1 to 3 kg/ton are preferred.
• the weight ratio between the total amount of the cationic retention agents, ie polyacrylamide and starch, and polymeric silicic acid can vary within wide limits depending on the composition of the stock, the presence of filler etc.. Usually the ratio of polyacrylamide+starch to polymeric silicic acid, calculated as Si ⁇ 2, is above 0.1:1, suitably above 1:1. The upper limit is not critical but is mainly decided from reasons of economy. A weight ratio between (polyacrylamide + starch) and polymeric silicic acid within the range of from 1:1 to 100:1 is preferred.
• the weight ratio between cationic starch and cationic polyacrylamide should be within the range of from 0.5:1 to 200:1.
• the weight ratio is suitably within the range of from 2:1 to 100:1 and preferably from 4:1 to 50:1.
• the improvement of the retention and dewatering through the disclosed process is obtained over a pH of the stock of from about 4 to about 10.
• the three components can be added to the fiber suspension in arbitrary order.
• the position for the addi ⁇ tions is not critical, but it is preferred not to add the polyacrylamide to the stock in an early stage of the paper production since it is sensitive to the type of mechanical stress which, for example, occurs in mixing apparatus.
• a particular improvement in comparison with known technique is obtained if the cationic starch is added to the stock first, followed by the cationic polyacrylamide and then the polymeric silicic acid.
• the three component system according to the invention can be used for production of paper from different kinds of stocks containing cellulose fibers.
• the three component system can for example be used for stocks from fibres -from chemical pulp, such as sulphate and sulphite pulp, thermo- mechanical pulp, refiner mechanical pulp or groundwood pulp, from as well hardwood as softwood.
• the system can of course also be used for stocks based on recycled fibres. Particularly good results have been obtained with stocks which are usually considered as difficult, namely both such which contain comparatively high amounts of non-cellulose substances such as lignin and dissolved organic materials, for example different types of mechanical pulps such as groundwood pulp, and such which contain recycled fibers.
• the combination according to the invention is thus par- ticularly suitable for stocks containing at least 25 per cent by weight of mechanical pulp and/or pulp from recycled fibers, based on the amount of dry pulp.
• paper and paper production which are used herein do of course include, in addition to paper and paper production, other cellulose fiber containing products in sheet or web form and their preparation, for example pulp sheets, board and paper board.
• the present combinations can of course be used in the production of paper in combination with other conventional additives for papermaking such as hydrophobing agents, dry strength agents, wet strength agents etc.. It is particu ⁇ larly suitable to use aluminum compounds in combination with the polymeric silicic acid and the two cationic polymers since it has been found that these can give a further improvement of retention and dewatering.
• Any for papermaking per se known aluminum compound can used, for example alum, polyaluminum compounds, aluminates, aluminum chloride and aluminum nitrate.
• the amount of aluminum compound can vary within wide limits and it is suitable to use the aluminum compound, calculated as AI2O3, in a weight ratio to the polymeric silicic acid, calculated as Si ⁇ 2. of at least 0.01:1.
• the ratio suitably does not exceed 3:1 and is preferably within the range of from 0.02:1 to 1.5:1.
• the polyaluminum compounds can for example be polyaluminum chlorides, polyaluminum sulfates and polyaluminum compounds containing both chloride and sulfate ions.
• the polyaluminum compounds can also contain other anions than chloride ions, for example anions from sulfuric acid, phosphoric acid, organic acids such as citric acid and oxalic acid.
• CSF Canadian Standard Freeness
• the polymeric silicic acid was prepared from water glass (Na2 ⁇ .3.3 ⁇ i ⁇ 2) which was diluted with water to an Si ⁇ 2 content of 5 per cent by weight.
• the aqueous solution was ion exchanged with ion exchange resin Amberlite IR-120 to a pH of 2.3.
• the specific surface area of the obtained acid polymeric silicic acid was measured by titration according to the method given earlier and was found to be 1450 m 2 /g.
• Test 7 shows the using a combination of polymeric silicic acid, cationic polyacrylamide and cationic starch. Even when the addition of polymeric silicic acid is reduced the effect is clearly better than when only two of the components are used, as evident from test 8. Tests 9 and 10 show that also the addition of polyacrylamide and starch can be reduced without any drastic reduction of the positive effect.
• Example 2
• the stock was composed of 60% bleached birch sulphate and 40% bleached pine sulphate.. 30% of chalk were added to the stock as filler. 1 g/1 of Na 2 SO 4 .10H 2 O was added. The concentration of the stock was 5 g/1 and the pH was 7.5. The fines fraction was 30.3%.
• the polymeric silicic acid was a polymeric silicic acid prepared from water glass using ion exchange resin for preparation of an acid sol that had been stored for a day and night as a 5% solution and then diluted to a concentra ⁇ tion of 1% and then further stored for 3 days and nights before use.
• the specific surface area for the polymeric silicic acid was 1500 m /g.
• the chemicals were added in the order starch, polyacrylamide and polymeric silicic acid.
• a comparison was also made with a commercial silica sol which had been alkali stabilized to a molar ratio ⁇ i ⁇ 2:Na2 ⁇ of about 40 and which had particles with a specific surface

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Paper (AREA)
• Polarising Elements (AREA)

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• 1989
  • 1989-11-09 SE SE8903752A patent/SE8903752D0/xx unknown
• 1990
  • 1990-10-24 CA CA002069308A patent/CA2069308C/en not_active Expired - Lifetime
  • 1990-10-24 AU AU67328/90A patent/AU637850B2/en not_active Expired
  • 1990-10-24 DE DE91900405T patent/DE69003249T2/de not_active Expired - Lifetime
  • 1990-10-24 ES ES91900405T patent/ES2046040T3/es not_active Expired - Lifetime
  • 1990-10-24 AT AT91900405T patent/ATE94231T1/de not_active IP Right Cessation
  • 1990-10-24 JP JP2515828A patent/JPH04505351A/ja active Pending
  • 1990-10-24 EP EP91900405A patent/EP0500770B1/de not_active Expired - Lifetime
  • 1990-10-24 WO PCT/SE1990/000688 patent/WO1991007543A1/en active IP Right Grant
• 1992
  • 1992-05-06 FI FI922055A patent/FI100611B/fi active

Non-Patent Citations (1)

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