TW527318B - Silica-based sols - Google Patents

Abstract

The invention relates to an aqueous sol containing silica-based particles which has an S-value within the range of from 10 to 45%, a viscosity within the range of from 5 to 40 cP, and a molar ratio of SiO2 to M2O, where M is alkali metal or ammonium, within the range of from 10:1 to 40:1, or a silica content of at least 10% by weight. The invention further relates to a process for the production of silica-based particles comprising the steps of (a) acidifying an aqueous silicate solution to a pH of from 1 to 4 to form an acid sol, (b) alkalising the acid sol at an SiO2 content within the range of from 4.5 to 8% by weight to, (c) allowing particle growth of the alkalised sol for at least 10 minutes, or heat-treating the alkalised sol at a temperature of at least 30 DEG C, and then (d) alkalising the obtained sol to a pH of at least 10.0. The invention further relates to silica-based particles obtainable by the process, the use of the silica-based particles as drainage and retention aids in the production of paper as well as a process for the production of paper from an aqueous suspension containing cellulosic fibres, and optional filler, in which silica-based particles and at least one charged organic polymer are added to the cellulosic suspension.

Description

527318 A7 B7 V. Description of the invention (ί) The present invention relates generally to a silica-based sol suitable for papermaking. More specifically, the present invention relates to a silica-based sol and silica-based particles, their production, and their use in the production of paper. The method of the present invention provides two kinds of silica-based particles and a sol containing silica-based particles, which has the characteristics of high drainage and water retention, high stability, and high solid content. Background In papermaking technology, aqueous suspensions containing cellulose fibers and optional fillers and additives are called stocks and are fed into a headbox, which injects the raw materials into a net. . Water is drained from the raw material through the web, so that a wet web of paper is formed on the web, and the paper web is further dehydrated and dried in the dry part of the paper machine. The drainage and water holding auxiliary customary land is introduced into the raw material to accelerate drainage and increase the adsorption of fibrous fibers by the fine particles, so that it maintains the fibers on the tube. The combination of silica-based particles and charged organic polymers is widely used as a drainage and water-holding aid. The organic polymers are like anionic and cationic acrylamide-based polymers, and cationic and amphoteric. Starch. Such additive systems are disclosed in U.S. Patent Nos. 4,388,150, 4,961,825 '4,980,025, 5,368,833, 5,603,805, 5,607,552, and 5,858,174; and International Patent Application WO 97/18351. These systems are among the most effective drainage and water holding aids in use today. Suitable for silica-based particles used for drainage and water-holding assistance. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) nmni I in a mouth T an Hi nn I I I »Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Employees' Cooperatives of the Ministry of Economic Affairs and Intellectual Property Bureau's printed by the Consumers' Cooperatives of the Ministry of Economic Affairs 527318 A7 B7 The water-soluble colloidal suspension is supplied as a so-called sol. Commercially used silica-based sols usually have a silica content of about 7 to 15% by weight and contain particles with a specific surface area of at least 300 square meters per gram. Sols with a higher specific surface area and dominated by silica-based particles are usually diluted to improve storage stability and avoid gel formation. It can superiorly provide silica-based sols and particles, which have further improved drainage and water holding performance, and have better stability. It is also capable of providing a method for preparing silica-based sols and particles, which has improved drainage, water retention, and stability properties. It is also superior in being able to provide a papermaking method with improved drainage and / or water retention. The present invention According to the present invention, silica-based sols and particles are provided, which are suitable for use as coagulants in water purification, and as drainage and water-holding aids for papermaking. The silica-based sols and particles according to the present invention show good stability over a prolonged period of time, especially high surface area stability and high stability to gels, and therefore they can have high specific surface areas and High silica concentration to prepare and transport. The sol has improved capabilities to maintain a high specific surface area stored at high silica concentrations. When used with anionic, cationic, and / or amphoteric organic polymers, the silica-based sols and particles further result in very good or improved drainage and water retention. Therefore, the present invention can increase the speed of the paper machine and use a lower dose of additives to produce a corresponding drainage and / or water holding effect, thus leading to an improvement. 5 The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) * (Please read the notes on the back before filling out this page) Binding ·-527318 A7 B7 Printed by the Intellectual Property Bureau Employees Consumer Cooperatives of the Ministry of Economic Affairs 5. Papermaking methods and economic benefits of the invention (>) . Therefore, the present invention relates to a silica-based particle and a water-soluble sol containing silica-based particles, which is also referred to herein as a silica-based sol, and its production, and further attached applications Patent scope. β The present invention also relates to the use of silica-based sols and particles, as an aid to drainage and water retention in papermaking, preferably in combination with the organic polymers described herein, as further described in the attached application Patent scope. As used herein, the term "drainage and water-holding aid" means one or more components (auxiliaries, reagents, or additives) that, when added to papermaking raw materials, produce more than when no such component is added. The result is better drainage and / or water retention. The present invention further relates to a method for producing paper from a water-soluble suspension containing fibrous fibers and an optional filler, forming and discharging the suspension on a net, comprising adding to silica-based particles Suspension, and at least one charged organic polymer. The invention therefore relates to a method, as further defined in the scope of the attached patent application. The silica-based sol according to the present invention is a water-soluble sol, which includes anion particles mainly composed of silica, and g 卩: particles mainly composed of silica (SiO 2) or silicic acid. The particles are preferably colloidal, β 卩: particle size in the colloidal range. The silica-based sol may have S- 値 in a range from 10 to 45%, suitably from 20 to 40%, and preferably from 25 to 35%. The S-fluorene can be measured and calculated as described by Iler and Dalton in J. Phys. Chem., Vol. 60 (1956), pages 955-957. The S- 値 indicates the degree of coagulation or microgel formation, and the lower S- 値 indicates a higher degree of coagulation. 6 (Please read the precautions on the back before filling out this page) 装 11! 11! 1

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 527318 A7 ______ B7 V. Description of the invention (bucket) The silica-based sol may have a molar ratio of 3102 to M20 of at least 10: In the range of 1 to 40: 1, suitably from 12: 1 to 35: 1, and preferably from 15: 1 to 30: 1, where M is an alkali metal ion (e.g., Li, Na, K) And / or ammonium. The silica-based sol may have a pH of at least 10.0, suitably at least 10.5, preferably at least 10.6, and most preferably at least 10.7. This pH can be as high as about 11.5, suitably as high as 11.0. The silica-based sol must suitably have a silica content of at least 3% by weight, but more suitably a silica content in the range from 10 to 30% by weight, and preferably from 12 to 25% by weight. In order to simplify transportation and reduce transportation costs, it is usually preferable to transport a high concentration of silica-based sol, but of course it is possible, and it is usually preferred to dilute and mix the silica-based sol before use. And particles to greatly reduce the content of silica, for example: the content of silica is at least 0.05% by weight, and preferably from 0.05 to 5% by weight Y. To improve the blending with equipment components. The viscosity of silica-based sols can vary depending on, for example, the silica content of the sol. Generally, the viscosity is at least 5 centipoise (cP), generally in the range from 5 to 40 centipoise, suitably 6 to 30 centipoise, and preferably 7 to 25 centipoise. The viscosity measured on a sol having a silica content of at least 10% by weight can be measured by known techniques, for example: using a Brookfield LVDV 11+ viscometer. The silica-based sol of the present invention is preferably stable. This means that these silica-based sols, when stored or aged for one month at 20 ° C in the dark and without stirring, 'show that if there is any, there is only a small amount in viscosity. increase. 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

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Printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs 527318 A7 ________ B7 V. Description of the Invention ($) The silica-based particles present in the sol suitably have an average particle size of less than about 20 nm, and are preferably The range is from about 1 to about 10 nm. As is commonly used in silica chemistry, particle size means the average size of the primary particles, which can be coagulated or non-agglomerated. The specific surface area of the silica-based particles is suitably at least 300 m 2 / g SiO 2, and preferably at least 550 m 2 / g SiO 2. Generally, this specific surface area can be as high as about 1050 square meters / gram, and suitably as high as 1,000 square meters / gram. In a preferred embodiment of the present invention, the specific surface area is in a range from 550 to 725 square meters / g, preferably from 575 to 700 square meters / g. In another preferred embodiment of the present invention, the specific surface area is in a range from 775 to 1050 square meters per gram. The specific surface area can be measured by NaOH titration in a known manner, for example: by Sears in Analytical Chemistry Vol. 28 (1956): Volume 12, pages 1981-1983, And as described in US Patent No. 5,176,891, after the proper removal or adjustment of any compounds present in the sample that would interfere with the titration, such as aluminum and boron species. The term "specific surface area" as used herein represents the average specific surface area of silica-based particles, and it is expressed in square meters per gram of silica (m2 / g SiO2). Therefore, in a preferred embodiment of the present invention, the silica-based sol has an S-S range from 20 to 40%, a viscosity from 7 to 25 centipoise, and a pH of at least 10.6. 'The molar ratio of Si02 to M20 is in the range of 15 to 30, the content of silica is at least 10% by weight' and the colloidal, anionic, silica-based particles contained have a specific surface area from 8 The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) 111111.

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527318 A7 B7 V. Description of Invention (G) (Please read the notes on the back before filling this page) 550 to 1050 square meters / gram. The silica-based sol according to the present invention has a silica content of from 15 to 20% by weight, and usually contains particles having a specific surface area of from 550 to 725 m 2 / g. However, according to the present invention, silica is used It is mainly soluble and has a silica content of from 10 to 15 weight ° /. The specific surface area that usually contains particles is from 775 to 1050 m2 / g. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In a preferred embodiment of the present invention, the silica-based solvent is almost free of aluminum, that is, there is no added modifier containing aluminum. In another preferred embodiment of the present invention, the silica-based sol is almost free of boron, that is, there is no added modifier containing boron. However, small amounts of these elements are present in the starting materials used to prepare silica-based sols and particles. In another preferred embodiment of the present invention, the silica-based sol is modified with different elements, such as aluminum and / or boron, which may be present in the water phase and / or silica-based In the particles. If aluminum is used, this sol may have a Moir ratio of Ai203 to 3 丨 02 in the range from 1: 4 to 1: 1500, suitably from 1: 8 to 1: 1000, and preferably from 1 : 15 to 1: 500. If boron is used, the sol may have a molar ratio of B to SiO2 in the range from 1: 4 to 1: 1500, suitably from 1: 8 to 1: 1000, and preferably from 1 :: 15 to 1: 500. If both aluminum and boron are used, the molar ratio of A1 to B is in the range from 100: 1 to 1: 100, suitably from 50: 1 to 1:50. The silica-based sol and particles according to the present invention can be produced from a conventional water-soluble silicate solution, such as starting from alkaline water glass, for example, potassium or sodium water glass, preferably sodium. Water glass. In sulphate solution or water 9 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 527318 A7 ____ B7 V. Description of the invention (1) The ratio of 3 丨 02 to M20 in the glass, Where M is an alkali metal ion, such as sodium, potassium, ammonium or a mixture thereof, suitably in the range from 1.5: 1 to 4.5: 1, preferably from 2.5: 1 to 3.9: 1. Appropriately used is a diluted silicate solution or water glass, which may have a true SiO2 content of from about 3 to about 12% by weight, preferably from about 5 to about 10% by weight. A silicate solution or water glass, which typically has a pH of about 13 or higher, is acidified to a pH of from about 1 to about 4. Acidification can be performed in a known manner by adding mineral acids, such as: sulfonic acid, hydrochloric acid, and phosphoric acid, or alternatively other chemicals known to be suitable for acidifying water glass, such as ammonium sulfate and carbon dioxide. When the mineral acid is added, the acidification is appropriately performed in two steps. The first * step is about pH 8 to 9, which has some maturity, that is, the growth of the particles, which is allowed to further acidify to pH from Occurs before about 1 to about 4. However, the acidification is preferably performed by an acid cation exchanger, which among other things results in a more stable product. Acidification is preferably performed by strong acid cation exchange resins, for example: sulfonic acids. It is preferred that the acidification proceed to a pH of from about 2 to 4, and most preferably from about 2.2 to 3.0. The resulting product, acid sol or polysilicic acid, contains silica-based particles with a high specific surface area, typically higher than 1000 m2 / g SiO2, and usually about 1300 to 1500 m2 / g SiO2. The acid sol is then basified, referred to herein as the first basification step. The first test step is performed by adding conventional tests, such as: lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide and mixtures thereof, and / or a water-soluble silicate solution as defined above. Potassium and sodium water glass, especially sodium water glass, has the molar ratio of Si0 2 to M20 as defined above. Appropriately 10 $ 1 ^ scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm)! Αν-(Please read the notes on the back before filling this page) Γ Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 527318 A7 B7 Printed by the Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Alkaliization step. The SiO2 content of the water glass solution used in the first alkalizing step is suitably used in a range from about 3 to about 35% by weight, and more preferably in a range from 5 to 30% by weight. The first test step is usually performed at a pH of at least 6, suitably at least 7, and preferably at least 5, and the pH is usually as high as 10.5, suitably as high as 10.0. The first alkalization step is further suitably carried out until the final SiO2 to M20 mole ratio is in a range from about 20: 1 to about 80: 1, preferably from 30: 1 to 70: 1, M is as defined above. The extent of the 'microsol' in the preparation of the sol as defined above can be influenced in several ways and controlled to the desired level. The degree of microsol can be affected by the salt content to adjust the preparation of the acid sol and the concentration in the first test step, because in this step, when the pH is about 5 and the minimum stability through the sol, the degree of microsol affected. In this process, it takes a long time to guide the degree of microsol to the desired level. It is particularly appropriate to control the degree of the microsol by adjusting the dry content and the content of SiO2 in the first alkalinization step, and to give lower thorium by a higher dry content. Keeping the Si02 content in the first alkalizing step in the range from 4.5 to 8% by weight, S- 値 can be controlled to the desired 値, for example: from 10 to 45 ° / (). In order to obtain a sol having an s-fluorene range from 20 to the range, the SiO 2 content in the first alkalinization step is appropriately maintained in the range from 5.0 to 7.5% by weight. Existing in the alkalization in the first alkalization step The silica-based sol in the sol is then grown by particles to obtain particles with lower specific surface area and higher stability. The method of particle growth must be properly performed to provide sand-based particles 11 with a specific surface area of at least 300 square meters per gram Si0 (please read the precautions on the back before filling this page). —111 — —.

This paper size is in accordance with China National Standard (CNS) A4 specification (21〇X 297 mm) 527318 A7 __B7 ____ V. Description of the invention (1) < Please read the notes on the back before filling this page), and it is better The ground is at least 550 square meters / gram and is as high as about 1050 square meters / gram and suitably as high as 1000 square meters / gram, especially as high as 950 square meters / gram Si02. In a preferred embodiment of the present invention, the granulation method is performed by providing granules having a specific surface area ranging from 550 to 725 m 2 / g SiO 2. In another preferred embodiment of the present invention, the particle growth method is performed to provide particles having a specific surface area ranging from 775 to 1005 square meters / gram 3o02. The reduction in surface area can be obtained by storing at room temperature for a slightly longer time, one day or up to about two days and nights, or preferably by heat treatment. In heat treatment, time and temperature can be adjusted to allow shorter times to be used at higher temperatures. It is of course even possible to use rather high temperatures for very short periods of time, and from a practical standpoint, it is more appropriate to use lower temperatures for slightly longer periods of time. In the heat treatment, the alkalized sol must be appropriately heated to a temperature of at least 30 ° C, suitably from 35 to 95 ° C, and preferably from 40 to 80 ° C. The heat treatment must be appropriately performed for at least 10 minutes, suitably from 15 to 600 minutes, and preferably from 20 to 240 minutes. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs After the particle growth step and optional cooling, the resulting silica-based sol is alkalized again, which is referred to herein as the second alkalization step. This second alkalizing step can be performed by adding conventional bases, for example: lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide and mixtures thereof, and / or a water-soluble silicate solution as defined above. Potassium and sodium water glass, especially sodium water glass with a ratio of 3 to 02 to M20 as defined above, are suitable for use in the second alkalizing step. The Si02 content of the water glass solution used in the second alkalizing step is suitably within a range from about 3 to about 35% by weight 'and 12 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 527318 A7 B7 5. Description of the invention (β) and preferably in a range from about 5 to about 30% by weight. The second alkalization step is suitably carried out to a pH of at least 10.0, suitably at least 10.5, more preferably at least 10.6, and most preferably at least 10.7. The pH can be as high as about 11.5 ', suitably as high as ii.o: the second alkalinization step is further suitably performed to the final 3, and the molar ratio of 02 to M20 is in a range from about 10: 1 to 40: 1, And suitably from 12: 1 to 35: 1, preferably from 15: 1 to 30: 1, M is as defined above. If desired, the method according to the invention also comprises a silica-based sol concentrate obtained after the second alkalizing step. In addition, or in addition, the alkalized sol obtained after the first alkalization step but before the particle growth or heat treatment step, or the sol after the particle growth or heat treatment step but after the second alkalization step. Can be concentrated. Concentration can be performed in known ways, for example: by osmosis, evaporation and ultrafiltration. Concentration is suitably performed to achieve a silica content of at least 10% by weight, preferably from 10 to 30% by weight, and more preferably from 12 to 20% by weight. / 〇. If desired, silica-based sols and particles can be added with compounds containing, for example, aluminum and / or boron. Suitable aluminum-containing compounds include aluminates such as: sodium aluminate and potassium aluminate, suitably sodium aluminate. The aluminum-containing compound is suitably used in the form of an aqueous solution. Suitable boron-containing compounds include boric acid, borate, such as: sodium and potassium borate, suitably sodium borate; tetraborate, such as: sodium and potassium tetraborate, suitably sodium tetraborate; and metaborate , Like: sodium metaborate and potassium. The boron-containing compound is suitably used in the form of an aqueous solution. When using an aluminum-containing compound in this method 'in the second alkalization step 13 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) Loaded

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 527318 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (M) Before or after the particle growth or heat treatment, it is appropriately added to the sol . In addition, or in addition, the aluminum-containing compound may be added to the silicate solution to acidify, to the acid sol, or to the alkalized sol obtained in the first base 4: step before the particle growth or heat treatment step. The aluminum-containing compound may be added in a mixture with the acid in the acidification step, and in a mixture with the base or the silicate solution in any one of the alkalinization steps. The appropriate addition amount of the aluminum-containing compound is such that the obtained sol has a molar ratio of A1203 to Si2O as defined above. When a boron-containing compound is used in the method, it is suitably added to the sol when particle growth or heat treatment is applied before or after the second alkalizing step. In addition, or in addition, the boron-containing compound may be added to the silicate solution to acidify, to the acid sol, or to the alkalized sol obtained in the first alkalizing step before the particle growth or heat treatment step. The boron-containing compound can be added as a mixture with the acid in the acidification step and as a mixture with the base or silicate solution in any one of the alkalination steps. A suitable addition amount of the boron-containing compound is such that the obtained sol has a molar ratio of B to Si20 as defined above. If both aluminum-containing and boron-containing compounds are used, their proper amount of addition is such that the resulting sol has a molar ratio of A1 to B as defined above. Prior to any modification of aluminum and / or boron, if the sol contains too high amounts of alkali metal or ammonium ions, it is preferred to remove at least a portion of these ions, for example: ion exchange to provide The silica-based sol has a final molar ratio of 8 to 02 to M20 within the desired range as defined above. 14 • nnnnn 1— an n I ϋ f— «nnn Hi nnn a · n Hi n —mm nn-(Please read the precautions on the back before filling this page). # · This paper size applies Chinese National Standards (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527318 A7 _ B7 V. Description of the invention (>) According to the present invention, silica-based sols, after optional concentration It has a silica content of from 10 to 30% by weight, suitably from 12 to 20% by weight, and a viscosity of at least 5 centipoise, generally in the range from 5 to 40 centipoise, and suitably 6 to 40 centipoise. 30 centipoise, and preferably from 7 to 25 centipoise, it can be prepared and the sol produced exhibits good storage stability and can be stored for several months without any significant reduction in specific surface area and without gum. The silica-based sols and particles according to the present invention are suitably used as coagulants, for example: in paper awards and paper production, especially as an auxiliary for drainage and water holding, and in water purification In the field, it is used for the purification of different kinds of wastewater, and especially for the purification of white foaming water from the pulp and paper industry. Silica-based sols and particles can be used as flocculants, especially as drainage and water retention aids, in combination with organic polymers that can be selected from anionic, zwitterionic, nonionic, and cationic polymers and mixtures thereof. It is also referred to herein as the "main polymer". This polymer is well known in the art for use as a flocculant and as a drainage and water retention aid. The polymer may be derived from natural or synthetic sources, and it may be linear, branched, or crosslinked. Examples of generally applicable main polymers include anionic, amphoteric, and cationic starches; anionic, amphoteric, and cationic guar gums, as well as anionic, amphoteric, and cationic polymers based on allylamine, and cationic poly ( Diallyl dimethyl ammonium chloride), cationic polyethyleneimine, cationic polyamines, cationic polyamines and polymers based on vinylamine, melamine-formaldehyde and urea_ formaldehyde resin , Appropriate silica-based sol, and at least one cation 15 ϋ · n I ϋ 1 ϋ n mi n. · N an nnn an n Order ----- (Please read the precautions on the back before filling in this (Page) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is a cationic polymer. Cationic starch and cationic polyacrylamide are particularly preferred polymers, and they can be used alone, together with other polymers, or with other polymers, such as other cationic polymers or anionic polyacrylamide. The molecular weight of the main polymer is suitably 1,000,000 or more, and preferably 2,000,000 or more. The upper limit is not important; it may be about 50,000,000, usually 30,000,000, and suitably about 25,000,000. However, polymer molecules derived from natural sources can be higher. When this silica-based sol and particles are used in combination with the above-mentioned main polymer, it is further preferable to use at least one low molecular weight (hereinafter referred to as LMW) cationic organic polymer, which is generally referred to as combined use Be an Anion Garbage Collector (ATC). ATC is known in the art as a neutralizing and / or fixing agent for harmful anionic substances present in the raw material, and it is used in combination with drainage and water holding aids to provide further drainage and / or water holding. LMW's cationic organic polymers may be derived from natural or synthetic sources, and are preferably LMW synthetic polymers. Suitable such organic polymers include LMW highly charged cationic organic polymers such as: polyamines, polyamidoamines, polyethyleneimines, based on diallyldimethylammonium chloride Homo- and copolymers, (meth) acrylamide and (meth) acrylic esters. The molecular weight of the LMW cationic organic polymer is relatively low relative to the molecular weight of the main polymer; it is suitably at least 1,000, and preferably at least 10,000. The upper limit of the molecular weight is usually about 700,000, suitably about 500,000, and usually about 200,000. Preferred combinations of polymers that can be shared with the silica-based sol of the present invention include 丄 MW cationic polymers and 16 paper sizes that are applicable to China National Standard (CNS) A4 (210 X 297 mm) ----- II --I ------ 1--I ^ · I ---- III (Please read the notes on the back before filling out this page) 527318 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Explanation (A) Combination of main polymers, for example, for example: cationic starch and / or cationic polyacrylamide, anionic polyacrylamide, and cationic starch and / or cationic polyacrylamide, and anionic polymer The combination of acrylamide. The drainage and water holding auxiliary components according to the present invention can be added to the raw materials in a conventional manner and in any order. When using silica-based particles and the drainage and water-holding aids of organic polymers such as main polymers, it is preferred to add the polymer to the raw material before adding silica-based particles , Even if the reverse order of addition is available. It is further preferred to add the main polymer before the shearing stage, which can be selected from pumping, mixing, cleaning, etc., and to add silica-based particles after the shearing stage. When used, the LMW cationic organic polymer is preferably introduced into the raw material before introduction into the main polymer. In addition, the LMW cationic organic polymer and the main polymer may be introduced into the raw material at the same time, or introduced separately, or as a mixture, for example: as disclosed in US Patent No. 5,858,174, which is hereby incorporated herein by reference. The LMW cationic organic polymer and the main polymer are preferably introduced into the raw material before the silica-based particles are introduced. In a preferred embodiment of the present invention, silica-based sols and particles are combined with at least one organic polymer as described above and at least one aluminum compound to be used as a drainage and water retention aid. Aluminum compounds can be used to further improve the drainage and / or water retention performance of raw material additives, which contain silica-based particles. Suitable aluminum salts include alum, aluminate, aluminum chloride, aluminum nitrate, and polyaluminum compounds, such as: Polychloride 17 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) --- --------- Installation · --- (Please read the precautions on the back before filling this page) Oh — III · •% 527318 A7 _____ B7 V. Description of the invention (κ) (Please read the back first Please fill out this page again) Aluminum, polyaluminum sulfate, polyaluminum compounds containing both chloride and sulfate, polyaluminosilicate-sulfate, and mixtures thereof. Polyaluminum compounds can also contain other anions, for example: anions from phosphoric acid, organic acids, such as citric acid and oxalic acid. Lujia's aluminum salts include sodium aluminate, alum, and polyaluminum compounds. The aluminum compound can be added before or after the silica-based particles are added. In addition, or in addition, the aluminum compound may be added simultaneously with a silica-based sol at the same point if necessary, or added alone or in a mixture therewith, for example: as disclosed in US Patent No. 5,846,384, which It is hereby incorporated by reference. In many cases, it is often appropriate to add an aluminum compound to the raw material early in the process, such as before other additives. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the components for drainage and water holding auxiliary according to the present invention, which can be added to the raw materials for dehydration, and the amount can vary within wide limits, especially depending on the type of component and Number, type of equipment, content of fillings, types of fillings, adding points, etc. Generally, the amount of the component added is better than that obtained without the component to produce better drainage and / or water retention. Sand-based sols and granules are usually added in an amount of at least 0.001% by weight, often at least 0.005% by weight, based on Si02 and based on dry raw material substances, that is: cellulose fibers and optional concrete Filling, and the upper limit is usually 1.0%, and suitably 0.5% by weight. The main polymer thorn is usually added in an amount of at least 0.001%, often at least 0.005% by weight, based on the raw material substance, and the upper limit is usually 3%, and suitably 1.5% by weight. When LMW cationic organic polymers are used in this method, the amount of summer that can be added is at least 0.05% of weight. 'Dried matter of raw materials to be dehydrated 18 ^ Paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 527318 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (A) Quality-based. A suitable portion range is from 0.07% to 0.5%, and a preferred range is from 0.1 to 0.35%. When an aluminum compound is used in this method, the total amount to be introduced into the raw material to be dehydrated depends on the kind of the aluminum compound used and other effects desired therefrom. For example, it is well known in the art to use aluminum compounds as rosin-based sizing agents. The total amount added is usually at least 0.05%, calculated on A1203 and based on dry raw material. A suitable serving size is from 0.1 to 3.0%, and a preferred range is from 0.5 to 2.0%. Other additives conventionally used in papermaking can of course be used in combination with the additives according to the invention, for example: dry strengthening agents, wet strengthening agents, optical luminescent agents, dyes, sizing agents, such as rosin-based Sizing agents and sizing agents that are reactive with cellulose, such as alkyl and alkenyl ketene dimers and ketene polymers, alkyl and alkenyl succinic anhydride, and the like. Cellulose suspensions or raw materials can also contain conventional types of mineral fillers, such as kaolin, Chinese clay, titanium dioxide, gypsum, talc, and natural and synthetic calcium carbonate, such as chalk, powdered marble, and precipitated Calcium carbonate. The method of the invention can be used to produce paper. The term "paper" as used herein, of course, includes not only paper and its products, but also other cellulose fiber sheets or net products, such as, for example, cardboard and paperboard, and their products. This method can be used to produce paper from different types of cellulose-containing suspensions, and the suspensions must suitably contain at least 25% by weight, and preferably at least 50% by weight, of such fibers on a dry matter basis. The suspension can be based on the fibers of chemical pulp, for example: sulfate, sulfurous acid 19 (Please read the precautions on the back before filling this page).

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This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 527318 A7 B7 V. Description of the invention (q) Salt and other organic dissolved pulp; mechanical pulp, such as UU cooked mechanical pulp, chemical- Thermomechanical pulp, refined pulp; and ground wood paper purple, from hardwood and softwood, and recycled fibers are also available. From there, you can choose pulp from ink removal, and mixtures thereof. Suspensions and stomachs can range from about 3 to about 10. The pH is suitably in the range of 3 5 and preferably from 4 to 9. 5 The invention is further illustrated in the following examples, however, it is not intended to be the same. Parts and% correspond to parts by weight and unless otherwise stated. ° Example 1 A standard silica sol was prepared as follows: 7617 grams of sodium water glass had a Mohr ratio of SiO2 to N ^ 0 of 3.3 and a SiCh content of 27.1%, diluted with water to 3,000 grams, to produce silicon. The acid salt solution (I) had an SiO 2 content of 6.9% by weight. 2800 g of this silicate or water glass solution was passed through a column saturated with hydrogen ions and filled with a strong cation parent exchange resin. 2450 grams of ion-exchanged water glass or polyacid (II) had a SiO 2 content of 6.5% by weight and a pH of 2.4 and were collected from an ion exchanger. 1988 grams of polysilicic acid (II) was fed into the reactor and diluted with 12.3 grams of water. Then 173.9 grams of a 6.9% silicate solution was added with vigorous stirring. The resulting solution was then heated at 85 ° C for 60 minutes and then cooled to 20 ° C. The obtained silica sol (la) has the following characteristics: 20 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇X 297) (please read the precautions on the back before filling this page) ei-i · nnnnnn · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527318 A7 B7 V. Description of the invention (π) Tannin (la) (reference) · · Si02 content = 7.3% by weight, Si02 / Na20 molar ratio ( Please read the precautions on the back before filling this page) = 40, pH = 10.2, S- 値 = 29%, viscosity = 2.2 centipoise, and specific surface area = 530 m2 / g. Production of two additional silica right sols, sol lb and sol lc, which have the following characteristics: Sol (16) (reference): 8 丨 02 content = 7.3% by weight, 3: 102 / valence 20 mole ratio = 63, pH = 10.0, S_ 値 = 26%, viscosity = 2.7 centipoise, and specific surface area = 500 m2 / g. Sol (lc) (reference): Si02 content = 5.4% by weight, Si02 / Na20 molar ratio = 35, pH = 9.8, S_ 値 = 32%, viscosity = 1.6 centipoise, and specific surface area = 690 square centimeters Feet / gram. Example 2 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed six silica-based particles of the sol according to the present invention prepared from polysilicic acid, similar to polysilicic acid (II) produced by the same ion exchange process And the Si02 content was 5.46% by weight. Under vigorous stirring, 1.46 kg of sodium water glass having a Si02 / Na20 ratio of 3.3 was added to 102.0 g of polysilicic acid, and the resulting solution had a Mo02 ratio of Si02 / Na20 of 54.0. This solution was heat-treated at 60 ° C for 2 hours and 20 minutes and cooled to 20 ° C, and then the product was now concentrated to a Si02 content of 15.6% by weight. The intermediate sol product is now divided into six separate samples, a to f. Samples a to c were further alkalized with NaOH, and samples d to f were alkalized with water glass to achieve a sol with a Si02 / Na20 mole ratio between 21.5 and 34.0, and the silica content was approximately 15.0% by weight. The obtained solution based on silica-based granules 21 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 527318 Α7 B7 5. Description of the invention (d) The glue has the characteristics described in Table 1: Table 1 Sol-Mole ratio [Si02 / Na20] pH S- 値 [%] Viscosity [centipoise] Specific surface area [square meter / g Si〇2] Sol 2a 21.5 10.7 31 17 720 Sol 2b 28.0 10.3 30 29 710 Sol 2c 34.0 10.0 29 40 690 Sol 2d 21.5 10.7 31 20 680 Sol 2e 28.0 10.3 29 34 670 Sol 2f 33.0 10.0 29 38 680 Example 3 As in Example 2, produced by the above-mentioned ion exchange method and alkalized to SiO2 with water glass The polysilicic acid (II) having a Mo / Na20 molar ratio of 54.0 was heat-treated at 60 ° C. for 1 hour. To 58 kg of this product was added 7.25 kg of diluted water glass having a Si02 / Na20 mole ratio of 3.3 and a silica content of 5.5% by weight. The obtained sol-sol 3 with silica-based particles was concentrated to a silica content of 15.2% by weight, and had a Mo02 ratio of Si02 / Na20 = 24, ρΗ = 10 · 7, S- 値 = 34, viscosity = 9.0 centipoise, and specific surface area = 760 m 2 / g Si02. Example 4 1000 g of polysilicic acid (II) having an SiO 2 content of 5.5% by weight, with vigorous stirring, with a SiO 2 content of 27 · 1% by weight, and having a SiO 2 / Na 20 molar ratio = 3.3 Mixing 14.5 grams of water glass resulted in a product with a Si02 / Na20 molar ratio of 51 and a sand content of 5.8% by weight Si02, which was heat-treated at 60 ° C for 1.5 hours, and then 22 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) · S · ϋ ϋ nnnn 01, i Hi «11 In I— Ha In s I · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527318 A7 B7 V. Description of the invention (/) (Please read the precautions on the back before filling out this page) After concentrating to sand and gravel containing 16.7% by weight Si02. The resulting 283 grams of product was mixed with 33.0 grams of NaOH, resulting in a silica-based particle of sol-sol 4 'having an Si02 content = 15.2% by weight, a Si02 / Na20 mole ratio = 21, and ρΗ = 10 · 6; S- 値 = 32%, viscosity = 14.2 centipoise, and specific surface area = 720 m 2 / g Si02. Example 5 The general procedure according to Example 3 was followed except that the heat treatment was performed for 1.25 hours and the concentration was carried out to a higher silica content. Two sols mainly composed of silica are prepared: sol 5a and sol 5b, sol 5a has an Si02 content = 18% by weight, a Si02 / Na20 mole ratio = 18, ρΗ = 10 · 7, and S- 値 = 36 %, Viscosity = 18 centipoise, and specific surface area = 700 m 2 / g. Sol 5b has a Si02 content = 20 weight. / 〇, Si02 / Na20 molar ratio = 18.3, PΗ = 10.7, S- 値 = 37%, viscosity = 31 centipoise, and specific surface area = 700 m 2 / g. Example 6 The performance of π drainage printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was evaluated by a Dynamic Drainage Analyser ('DDA), which can be obtained from AkHni (Sweden), Sweden. When the stopper is removed and the vacuum is applied to the other side of the pipeline opposite to the side where the raw material is present, it measures the time to discharge a fixed volume of raw material through the net. The raw material used is based on a mixture of 60% bleached birch sulfate and 40% bleached pine sulfate. 30% of honing carbonic acid is added to it. 1 1 sheet of size applies to the Chinese standard (CNS) A4 (210 X 297 mm) " 527318 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _______ B7 ^ ___ —____ 5. Description of the invention (d) Calcium is used as a filling. The volume of the raw material was 800 ml, the concentration was 0.25%, and the pH was about 8.0. The conductivity of the raw material was adjusted to 0.47 mS / cm by adding sulfuric acid. In the test 'a sand-based sol was used with a cationic polymer. Raisamy Dl42, which is a conventional and highly cationized powder, has a degree of substitution of 0.042, and its amount added to the raw material is 12 kg / metric ton. 4 of the silica-based sol 'was tested in this example. In addition, sol and 6b were also tested for comparison purposes. Sol 6a is a commercial silica' with S- 値 = 45% 'Si02 content = 15.0 Weight./G, Si〇2 / Na2 Moore ratio = 40, viscosity = 3.0 centipoise, specific surface area of the particles = 500 square meters / g. Sol 6b is another commercial silica sol With ^ 値 = 36%, Si02 content = 10.0 weight. / 〇, Si〇2 / Na2〇 Molar ratio = 10, viscosity = 2.5 centipoise, specific surface area of particles = 880 square meters / gram. With silicon The stone-based sol was added at a rate of 0.5 kg / metric ton, calculated on Si02 and based on a dry raw material system. Throughout the test, raw materials were placed in baffled bottles at a speed of 15,000 revolutions per minute. Stir and chemically add as follows: i) Add the cationic powder to the ingredients , Continued to stirred for 30 seconds, H) Silica-based sol was added to the original compound, followed by stirring for 15 seconds, III) starting material is discharged, while automatically recording the drainage time. The drainage time for different silica-based sols is shown in Table 2: 24 This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) 0 Pack ---- Order --------- ^ 0 527318 Α7 Β7 V. Description of the invention (Silicon-based roll glue dehydration time [sec] Sol la (reference) Sol lb (reference) Sol lc (reference) Sol 2d Sol 3 Sol 4 Sol 6a (Reference) Sol 6b (Reference) 12.0 11.1 12.0 9.7 9.5 9.4 12.0 9.8 Example printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 Evaluation of drainage according to the general procedures of Example 6 Performance, except that the raw material has a concentration of 0.3% and a pH of about 8.5. The water holding performance is evaluated by a suspension meter, and the turbidity of the filtrate and white foaming water obtained by discharging the raw material is measured. Invented, the silica-based sol according to Example 5 is used for comparison with sol 6a. Table 3 shows the drainage time obtained under different doses (kg / metric ton) of silica-based particles, in Si. 2 Calculated and based on dry raw material system. Only add yang Ionic starch (12 kg / metric ton, based on dry raw material system), the drainage time is 15.8 seconds. ____ Table 3 _ Silica-based sol drainage time (seconds) / turbidity (NTU), at Si02 —〇 · 5 kg / ton 1.0 kg / ton 1.5 kg / ton 2.0 kg Eagle 6 * 8 / 6〇5 · 7/53 6.0 /. 25 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ） -II I --—— 丨 丨 丨 ----- I-^ »11 (Please read the notes on the back before filling this page)

Claims (1)

A8B8C8D8 1. Silica-based particles of water-soluble sol, characterized by: S- 値 range from 10 to 45%, viscosity range from 5 to 40 centipoise, and 3 丨 02 to M20 The molar ratio is in the range from 10: 1 to 40: 1, where M is an alkali metal or ammonium, and the silica-based particles have a specific surface area of 300 to 1050 square meters per gram. Within range. 2. Silica-based particles of water-soluble sols, which are characterized in that they have an S- 値 range from 10 to 45%, a viscosity range from 5 to 40 centipoise, and a silica content range from 3 to 30% by weight, and the silica-based particles have a specific surface area in a range of 300 to 1050 square meters / gram. 3. The water-soluble sol according to item 1 of the scope of the patent application, wherein the content of the sand-sol has a range of 3 to 30% by weight. 4. The water-soluble sol according to any one of claims 1, 2 or 3 of the patent application range, wherein the silica-based particles have a specific surface area ranging from 775 to 1050 square meters / gram. 5. The water-soluble sol according to any one of the claims 1, 2, or 3, wherein the silica-based particles have a specific surface area ranging from 550 to 725 m 2 / g. 6. The water-soluble sol 'according to any one of claims 1, 2 or 3 of the scope of the patent application, wherein the range of S- 値 is from 20 to 40%. 7. A water-soluble sol according to any one of claims 1, 2 or 3 of the scope of the patent application, wherein the viscosity ranges from 7 to 25 centipoise. 8. The water-soluble sol according to any one of the claims 1, 2 or 3 of the scope of the patent application, wherein the meaning of the mol ratio of 02 to μ2 is between 15: 1 and the national standard (CNS) ) A4 specifications (21〇X 29 ^, love) (Please read the notes on the back before writing this page),-° line A8 B8 C8 D8 six 527318, patent application range to 30: 1, of which Μ It is an alkali metal or ammonium. 9. The water-soluble sol according to any one of claims 1, 2 or 3, wherein it has a pH of 10.0 to II · 5. 10. A method for preparing silica-based particles, which is characterized in that it comprises the following steps: U) acidifying an aqueous silicate solution to a pH of 1 to 4 to form an acid sol; (b) alkalizing the acid sol pH ranging from 6.0 to 10.0, the SiO2 content of the acid sol is in the range from 4.5 to 8% by weight; (c) allowing the particles of the alkalized sol to grow for at least 10 minutes; then (d) alkalizing the The resulting sol has a pH in the range of 10.5 to 11.5. 11. A method for preparing silica-based particles, comprising: (a) acidification. The pH of an aqueous silicate solution is from 1 to 4 to form an acid sol; (b) the content of alkalized SiO2 is from 4.5 (C) heat treating the alkalized sol at a temperature of at least 30 ° C; and (d) alkalizing the heat-treated sol to a pH ranging from 10.0 to 11.5. 12. A method according to item 10 or 11 of the scope of patent application, wherein the alkalinization according to (b) and (d) is performed by an aqueous silicate solution. 13. A method according to item 10 or 11 of the scope of patent application, wherein the particle growth and heat treatment according to (c) are performed at a temperature ranging from 35 to 95 ° C. 14. A method according to item 10 or 11 of the scope of patent application, wherein the particle growth and heat treatment according to (c) are performed for 20 to 240 minutes. (Please read the precautions on the back before copying this page) The size of the paper used for the booklet is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 527318 A8 B8 C8 D8 ___ 6. Application for patent scope 15. According to the application The method of item 10 or 11 of the patent scope 'wherein according to (d) alkalinization produces a silica-based sol having a molar ratio of 3 to 02 to M20 in the range of 15: 1 to 30: 1, where M It is an alkali metal ion or surface, and the pH is in the range of 10.0 to 11.5. 16. A silica-based particle obtainable by a method comprising the following steps: (a) acidifying the aqueous silicate solution to a pH of 1 to 4 to form an acid sol; (b) alkalizing the acid sol pH In the range of from 0.0 to 10.0, the SiO2 content of the acid sol is in the range from 4.5 to 8% by weight; (c) the particles of the alkalized sol are allowed to grow for at least 10 minutes; then (d) The pH of the obtained sol was in the range of 10.5 to 11.5. 17. The silica-based particles according to any of claims 1, 2, 3 or 16 of the scope of the patent application, which are used as drainage and water-holding auxiliary agents in paper production. 18. · A method for producing paper from a water-soluble suspension containing cellulose fibers and optionally a filler, which comprises adding silica-based particles and at least one charged organic polymer to the suspension, The suspension is formed and drained on a net, which is characterized in that the prominent particles mainly composed of silica are present in the water-soluble sol biosol according to any of items 1 to 9 of the scope of patent application, or by Applicable to the method of any one of the patent scope 10 to I5. 19. The method according to item 18 of the application, wherein the charged organic polymer is a cationic starch or a cationic polyacrylamide. 20. According to the method of any one of items 18 or 19 in the scope of patent application, ____— 3 ---__ This paper size applies to China National Standard (CNS) A4 (210x 297 mm)-~-(please first Read the notes on the back and fill in this page again) '1T ·· Line 527318 A8 B8 C8 D8 VI. Application for patent scope Where the silica-based particles are added to the suspension, the water-soluble sol is diluted or mixed with Water is mixed to form a water-soluble sol having a silica content from about 0.05 to 5% by weight. 21. The method according to any one of claims 18 or 19 of the scope of the patent application, wherein the amount of silica-based particles added to the suspension ranges from 0.005 to 0.5% by weight, calculated as SiO2 and dried Based on cellulose fibers and optional fillers. (Please read the precautions on the back before filling this page) This paper is again applicable to China National Standard (CNS) A4 (210 X 297 mm)