CN101476262A - Silica-based sols - Google Patents
Silica-based sols Download PDFInfo
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- CN101476262A CN101476262A CNA2009100038192A CN200910003819A CN101476262A CN 101476262 A CN101476262 A CN 101476262A CN A2009100038192 A CNA2009100038192 A CN A2009100038192A CN 200910003819 A CN200910003819 A CN 200910003819A CN 101476262 A CN101476262 A CN 101476262A
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Abstract
The invention relates to an aqueous sol containing silica-based particles with an S-value within the range of from 10 to 45 , viscosity from 5 to 40cP and SiO<SUB>2</SUB>/M<SUB>2</SUB>O mol ratio from 10:1 to 40:1, wherein M represents alkali metal or ammonium, or dinas rock at least 10by weight. The invention further relates to the method for producing silica-based particles, which comprises the following procedures: (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; (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 (d) alkalising the obtained sol to a pH of at least 10. 0. The invention further relates to the silica-based particles obtained from the method, and the silica-based particles are taken as a drainage and retention aid 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
Generality of the present invention relates to the silica-based sols that is suitable for papermaking.More specifically say, the present invention relates to silica-based sols and silica base particle, their production method and their purposes in papermaking.Method of the present invention provides silica base particle and has had high drainage and retention property, high stability and the highly filled colloidal sol that contains silica base particle.
Background
In field of papermaking, to contain cellulose fibre and optional filler and the water-borne dispersions (being called paper stock) of additive and feed in the head box (headbox), it is discharged to paper stock on the forming net.Water leaches through forming net from paper stock, so that form the further dehydration and dry of dryer section at paper machine of wet web (paper of wet web) and paper web on the net.Usually with drainage with keep auxiliary agent and be incorporated in the paper stock, so that help drainage and increase the absorption of fine grained to the cellulose fibre, so that they can be retained in the online fiber.
Silica base particle is widely used as drainage and keeps auxiliary agent with charged organic polymer image anion and cation acrylamide type polymer and CATION and amphoteric starch.In U.S. patent Nos.4,388,150; 4,961,825; 4,980,025; 5,368,833; 5,603,805; 5,607,552; With 5,858,174; And this additive system disclosed in the International Patent Application WO 97/18351.These systems belong to the most effective drainage of present use and keep auxiliary agent.
The silica base particle that is suitable as drainage and keeps auxiliary agent is normally with aqueous colloidal dispersions, i.e. the form supply of so-called colloidal sol.The colloidal sol of industrial use has the silica content of about 7-15wt% usually, contains specific area and is 300m at least
2The particle of/g.Colloidal sol with silica base particle of high-specific surface area more is normally rarer, to improve storage stability and to avoid gel to form.
It is desirable to, can provide to have further improved drainage and retention property and even the silica-based sols and the particle of better stability.Also it is desirable to, can be provided for preparing the silica-based sols with improved drainage, reservation and stability and the method for particle.Still it is desirable to, can provide to have the paper technology that improves drainage and/or reservation.
The present invention
According to the present invention, provide the flocculant that is suitable as in desalt and as the drainage in papermaking with keep the silica-based sols and the particle of auxiliary agent.According to silica-based sols of the present invention and particle performance the good stability in long-time, significantly high surface area stability and avoid the high stability of gel formation, therefore, they can prepare under high-specific surface area and high silica concentration and load and transport.This colloidal sol has the improvement ability that keeps high-specific surface area in the storage of high silica concentration.Silica-based sols and particle have further obtained very good or improved drainage and retention, when uniting use with anion, CATION and/or both sexes organic polymer.The invention enables speed that may increase paper machine and the additive that uses low dosage to obtain corresponding drainage and/or keep effect in view of the above, thereby produced improved paper technology and economic benefit.Therefore the present invention relates to silica base particle and contains the hydrosol of silica base particle, also is called silica-based sols and their production method here, as further defining in the claims.
As further defining in the appended claims, the invention still further relates to silica-based sols and particle, the organic polymer that preferred combination is described here is as the drainage in papermaking with keep the purposes of auxiliary agent.Here employed term " drainage and keep auxiliary agent " is meant one or more components (auxiliary agent, reagent or additive), in the time of in being added into paper making raw material, obtains better drainage and/or the retention compared when not adding these components.The invention further relates to and be used for the method for producing paper from the water-borne dispersions that contains the optional filler of cellulose fiber peacekeeping, it comprises silica base particle and at least a charged organic polymer is added in the suspension that suspension is shaped and drainage on the net.Therefore the present invention relates to the method as further defining in appended claims.
Silica-based sols according to the present invention is to contain anionic silica-based particles, promptly with silica (SiO
2) or silicic acid be the hydrosol of particle on basis.Particle is colloidal state preferably, promptly in the colloidal state scope of granularity.Silica-based sols can have at 10-45%, the S-value in suitable 20-40% and the preferred 25-35% scope.The S-value can be as Iler ﹠amp; Carry out measurements and calculations as described in the Dalton in J.Phys.Chem.60 (1956), 955-957.The degree that the S-value representation is assembled or microgel forms, low S-value has embodied higher concentration class.
Silica base particle can have from 10:1 to 40:1, and is suitable from 12:1 to 35:1 and preferred SiO in from 15:1 to the 30:1 scope
2With M
2The mol ratio of O, wherein M be alkali metal ion (for example, Li, Na, K) and/or ammonium.Silica-based sols can have at least 10.0, and suitable at least 10.5, preferred at least 10.6 and at least 10.7 pH value most preferably.This pH value can be up to about 11.5, suitable paramount 11.0.
Silica-based sols should suit to have the silica content of 3wt% at least, but preferably be that silica content is in the scope of 10-30wt% and preferred 12-20wt%.In order to simplify shipment and to reduce cost of transportation, general preferred shipment high concentration silica-based sols, but it is feasible that yes, usually preferably before use dilute with water and mix silica-based sols and particle with remarkable reduction silica content, for example, to 0.05wt% at least and preferred silica content in the 0.05-5wt% scope, so that improve and the mixing of furnish component.The viscosity of silica-based sols can change according to the silica content of for example colloidal sol.Usually, viscosity is 5cP at least, normally at 5-40cP, in the scope of suitable 6-30cP and preferred 7-25cP.Suitable can enough known technologies to having this viscosity that the colloidal sol of the silica content of 10wt% at least measures, for example use Brookfield LVDV II+ viscosimeter to measure.Preferred silica based sols of the present invention is stable.This means, when standing to store or aging one month the time, these silica-based sols have showed only slightly increasing of viscosity, as if the words that have at 20 ℃ under dark and the non-stirring condition.
The silica base particle that is present in the colloidal sol preferably has approximately below the 20nm and preferably in about 1 particle mean size that arrives in about 10nm scope.As common in the silica chemistry, granularity refers to the average-size of primary granule, and these primary granules can be to assemble or non-gathering.The specific area of silica base particle is suitably 300m at least
2/ g SiO
2, preferred 550m at least
2/ g.Generally, specific area can be paramount to about 1050m
2/ g and compatibly paramount to 1000m
2/ g.In a preferred embodiment of the invention, specific area is at 550-725m
2/ g, preferred 575-700m
2In the scope of/g.In another preferred embodiment of the present invention, specific area is at 775-1050m
2In the scope of/g.At any material of suitably removing or regulating the meeting interference titration that is present in the sample, resemble after aluminium and the boron substance, specific area can be passed through known way, for example use Sears in AnalyticalChemistry28 (1956): 12, among the 1981-1983 and at U.S. patent No.5, the method of describing in 176,891 is measured with the NaOH titration.Term used herein " specific area " represent silica base particle average specific surface area and with square metre/every gram silica represents (m
2/ g SiO
2).
In a preferred embodiment of the invention, therefore silica-based sols has the S-value in the 20-40% scope, the viscosity of 7-25cP, at least 10.6 pH, the SiO in the 15-30 scope
2With M
2The mol ratio of O, the silica content of 10wt% at least, and contain specific area at 550-1050m
2Colloidal state anionic silica-based particles in the/g scope.Have 15-20wt% silica content contain specific area usually at 550-725m according to silica-based sols of the present invention
2Particle in the/g scope, and have 10-15wt% silica content contain specific area usually at 775-1050m according to silica-based sols of the present invention
2Particle in the/g scope.
In a preferred embodiment of the invention, silica-based sols is substantially free of aluminium, does not promptly contain the modifier that contains aluminium of interpolation.In another preferred embodiment of the present invention, silica-based sols is substantially free of boron, does not promptly contain the additive that contains boron of interpolation.Yet a spot of these elements can be present in the initiation material that is used for preparing silica-based sols and particle.In another preferred embodiment of the present invention, silica-based sols uses various elements, and for example aluminium and/or boron come modification, and they can be present in water and/or the silica base particle.If use aluminium, colloidal sol can have at 1:4-1:1500, the Al in the scope of suitable 1:8-1:1000 and preferred 1:15-1:500
2O
3With SiO
2Mol ratio.If use aluminium and boron, the mol ratio of Al and B can be at 100:1-1:100, in the scope of suitable 50:1-1:50.
Can resemble buck glass from the normal silicate aqueous solution according to silica-based sols of the present invention and particle, for example potassium or sodium silicate, it is preferred that sodium silicate is initial produces.SiO in silicate emulsion or waterglass
2With M
2The mol ratio of O is suitably at 1.5:1-4.5:1, and in the scope of preferred 2.5:1-3.9:1, wherein M is an alkali metal, for example sodium, potassium, ammonium or their mixture.Be fit to use the silicate solutions or the waterglass of dilution, they can have the about 12wt% of about 3-, the preferably approximately SiO of the about 10wt% of 5-
2Content.Usually have about 13 or the pH that become about 1-about 4 by acidifying at silicate solutions or the waterglass of the pH more than 13.Acidifying can be in a known manner by the adding inorganic acid, for example sulfuric acid, hydrochloric acid and phosphoric acid, or optional and known other chemicals that is suitable for the acidifying of waterglass, and for example ammonium sulfate and carbon dioxide carry out.When adding inorganic acid, suitable the going on foot with two of acidifying carried out, and therefore the first step makes and before the pH that further is acidified to about 1-about 4 certain slaking, i.e. germination take place to the pH of about 8-9.Yet preferably, acidifying is undertaken by acid cationite, and in addition, this exchanger has obtained more stable product.Strong-acid cation-exchange resin, for example the carrying out of sulfonic acid type are preferably used in acidifying.Preferably, be acidified to the pH of about 2-4, more preferably the pH of about 2.2-3.0.Obtained product, promptly acid-sol or poly-silicic acid contain normally at 1000m
2More than/the g and usually at about 1300m
2The silica base particle of/g high-specific surface area up and down.
Acid-sol alkalizes then, is referred to as first alkalinization step here.First alkalinization step can be by adding conventional base, and for example the aqueous silicate solution of lithium hydroxide, NaOH, potassium hydroxide, ammonium hydroxide and their mixture and/or above definition carries out.SiO with above definition
2With M
2The potassium of O mol ratio and sodium silicate, especially sodium silicate is suitable for alkalinization step.The SiO that is used for the water glass solution of first alkalinization step
2Content is adapted in the about 35wt% scope of about 3-with preferably in the scope of 5-30wt%.First alkalization proceeds at least 6 usually, suitable at least 7 and preferred at least 7.5 pH, and this pH is fit to reach 10.0 usually up to 10.5.First alkalization further is fit to proceed to SiO
2With M
2The final mol ratio of O is that in the scope of preferred 30:1-70:1, wherein M as defined above at about about 80:1 of 20:1-.In the preparation of colloidal sol as defined above, the influence that the degree of microgelization can hard to bear several modes, and can be controlled to desirable value.The degree of microgel can hard to bear salt content, in the preparation of acid-sol and the influence of the concentration adjustment in first alkalinization step because in this step, when the stability that is used for colloidal sol when minimum is crossed (pH about 5), the degree of microgel is affected.Cross the time in stage by prolonging at this, the degree of microgel can be adjusted to required value.What especially be fit to is to be SiO by the dry content that is adjusted in first alkalinization step
2Content is controlled the degree of microgel, and wherein high dry content produces low S-value.By remaining on the SiO in first alkalinization step
2Content is in the scope of 4.5-8wt%, and the S-value can be controlled to for example desirable value of 10-45%.In order to obtain to have the colloidal sol of the S-value in the 20-40% scope, SiO in first alkalinization step
2Content is fit to remain in the scope of 5.0-7.5wt%.
The silica base particle that is present in the alkalization colloidal sol that obtains in first alkalinization step carries out germination then, so that the particle that acquisition has lower specific area and high stability.Should suit to carry out the germination method and be 300m at least so that specific area to be provided
2/ g and preferred 550m at least
2/ g and about at the most 1050m
2/ g and suitable 1000m at the most
2The silica base particle of/g.In a preferred embodiment of the invention, carry out the germination method to be provided at 550-725m
2Specific area in the/g scope.In another preferred embodiment of the present invention, carry out the germination method to be provided at 775-1050m
2Specific area in the/g scope.The decline of surface area can be by at room temperature storing the long time, one day to about two days two night or preferably obtain by heat treatment.In heat treatment, can regulate time and temperature so that under higher temperature, use the short time.Even if certainly in the very short time, use quite high temperature, from a practical viewpoint, be more suitable in the long time, using lower temperature.In heat treatment, alkalization colloidal sol should suit at least 30 ℃, heats under the temperature of suitable 35-95 ℃ and preferred 40-80 ℃.Heat treatment should suit to carry out at least 10 minutes, is fit to 15-600 minute and preferred 20-240 minute.
After germination step and optional cooling, the silica sol that obtains alkalizes once more, is referred to as second alkalinization step here.Second alkalinization step can be by adding conventional base, for example lithium hydroxide, NaOH, potassium hydroxide, ammonium hydroxide and their mixture and/or as defined above aqueous silicate solution carry out.Has SiO as defined above
2With M
2The potassium of the mol ratio of O and sodium silicate, especially sodium silicate is suitable for second alkalinization step.The SiO that is used for the water glass solution of second alkalinization step
2Content is adapted in the scope of the about 35wt% of about 3-and is preferred in the scope of 5-30wt%.Second alkalization proceeds at least 10.0 usually, and suitable at least 10.5, preferred at least 10.6 and 10.7 pH most preferably, this pH can be fit to reach 11.0 up to about 11.5.Second alkalization is fit to further proceed to SiO
2With M
2The final mol ratio of O is at about about 40:1 of 10:1-, suitable 12:1-35:1, and in the scope of preferred 15:1-30:1, wherein M is as defined above.
If desired, the method according to this invention can also comprise and is concentrated in the silica-based sols that obtains after second alkalinization step.As selecting or in addition, in the first alkalization back but the alkalization colloidal sol that obtained before germination or heat treatment step, perhaps the colloidal sol of acquisition can concentrate germination or heat treatment step after but before second alkalization.Concentrate and for example to be undertaken in a known manner by permeating method, evaporation and ultrafiltration.Concentrate to be fit to proceed to and obtain 10wt% at least, preferred 10-30wt% and the more preferably silica content of 12-20wt%.
If desired, silica-based sols and particle can come modification by adding the compound that for example contains aluminium and/or boron.The aluminum contained compound that is fit to comprises that aluminate resembles sodium aluminate and potassium aluminate, and suitable is sodium aluminate.Aluminum contained compound is fit to use with the form of the aqueous solution.The boron-containing compound that is fit to comprises boric acid, and borate resembles Boratex and potassium borate, and suitable is Boratex, and tetraborate resembles sodium tetraborate and dipotassium tetraborate, and suitable is sodium tetraborate, and metaborate resembles kodalk and potassium metaborate.The suitable form with the aqueous solution of boron-containing compound is used.
When using aluminum contained compound in the method, suited before or after second alkalinization step, it is added to carry out in germination or the heat treated colloidal sol.As selection, perhaps in addition, before germination or heat treatment step, aluminum contained compound can be added in the silicate solutions by acidifying, add in the acid-sol or additive in the alkalization colloidal sol that in first alkalinization step, obtains.Aluminum contained compound can be in acidification step mixes with acid and adds and mix adding with alkali or silicate solutions in arbitrary alkalinization step.Aluminum contained compound is fit to so that the colloidal sol that obtains has Al as defined above
2O
3With SiO
2The amount of mol ratio add.
When using boron-containing compound in the method, suited before or after second alkalinization step it is added to and carry out in germination or the heat treated colloidal sol.As selection, perhaps in addition, before germination or heat treatment step, boron-containing compound can be added in the silicate solutions with acidifying, be added in the acid-sol or the alkalization colloidal sol that in first alkalinization step, obtains in.Boron-containing compound can be in acidification step mixes with acid and adds, and perhaps mixes with alkali or silicate solutions in arbitrary alkalinization step and adds.Boron-containing compound is suitable so that the colloidal sol that obtains has B and SiO as defined above
2The amount of mol ratio add.If use aluminum contained compound and boron-containing compound simultaneously, they are fit to add so that the colloidal sol that obtains has the amount of the mol ratio of suitable as defined above Al and B.
Before any aluminium and/or boron modification,, preferably remove at least a portion of these ions, so that SiO to be provided by for example ion-exchange if colloidal sol contained the alkali metal ion or the ammonium ion of a large amount
2With M
2The final mol ratio of O be as the required scope of above definition in silica-based sols.
According to this method, can prepare after optional concentrating and have 10-30wt%, suitable is the silica content of 12-20wt%, at least 5cP, normally in the scope of 5-40cP, be suitably the silica-based sols of the viscosity of 6-30cP and preferred 7-25cP, the colloidal sol of being produced has showed excellent storage stability, can store some months, and can obviously not reduce specific area and not have gel to form.
Silica-based sols of the present invention and particle are suitable as flocculant, for example in the production of paper pulp and paper, especially can be used as drainage and keep auxiliary agent, and in the field of desalt, be used for the purifying and the special purifying that is used for from the plain boiled water of paper pulp and paper industry of inhomogeneity waste water.Silica-based sols and particle can be used as flocculant with the organic polymer that can be selected from anion, amphion, nonionic and cationic polymer and their mixture (also being referred to as " host polymer " here), especially as drainage and reservation auxiliary agent.This polymer is well-known as flocculant with as drainage with the purposes that keeps auxiliary agent in the art.Polymer can be obtained by natural or synthetic source, and they can be linear, branching or crosslinked.The example of the general host polymer that is fit to comprises anion, both sexes and cationic starch, anion, amphion and cation guar gum, and anion, both sexes and cation acrylamide type polymer, and CATION poly-(chlorination diallyl dimethyl ammonium), CATION polyethylene imine, cationic polyamine, daiamid and vinylamide type polymer, melamine-formaldehyde and urea-formaldehyde resins.What be fit to is, silica-based sols and at least a CATION or amphiphilic polymers, and the preferred cationic polymer is in conjunction with use.Cationic starch and cationic polyacrylamide are especially preferred polymer, they can be separately, mutually together or with other polymer, for example other cationic polymer or anionic polyacrylamide are used together.The molecular weight of host polymer suits 1,000, more than 000, preferably 2,000, more than 000.The upper limit is not strict with; It can be about 50,000,000, common 30,000,000 and be fit to about 25,000,000.Yet the molecular weight of the polymer that is obtained by natural origin can be higher.
When being used in combination silica-based sols and particle and above-mentioned host polymer, further preferred at least a low molecular weight (hereinafter LMW) cationic organic polymer that uses commonly is referred to as and is used as anionic trash trap (ATC).ATC is called as the neutralization and/or the fixative of the harmful anion material that is used for being present in paper stock in the art, they with drainage and keep being used in combination of auxiliary agent often provide drainage and/the further improvement of retention.The LMW cationic organic polymer can be obtained by natural or synthetic source, preferably the LMW synthetic polymer.This organic polymer that is fit to comprises cationic organic polymer that LMV is highly charged such as polyamine, daiamid, polyethylene imine, based on the equal and copolymer of chlorination diallyl dimethyl ammonium, (methyl) acrylamide and (methyl) acrylate.With respect to the molecular weight of host polymer, the molecular weight of LMW cationic organic polymer is preferably lower; It is normally at least 1,000 and preferably at least 10,000 years old.The upper limit of molecular weight normally about 700,000, suitable about 500,000 and usually about 200,000.Can comprise LMW cationic organic polymer and host polymer with the preferred combination thing of the common polymer that uses of silica-based sols of the present invention, for example the bond of the bond of cationic starch and/or cationic polyacrylamide, anionic polyacrylamide and cationic starch and/or cation acrylamide and anionic polyacrylamide.
Can will be added in the paper stock according to the component of drainage of the present invention and reservation auxiliary agent with any order in due form.When use comprises silica base particle and organic polymer, when for example the drainage of host polymer is with the reservation auxiliary agent, preferably before adding silica base particle, polymer is added in the paper stock, even if can use opposite interpolation order.Further preferably, can be selected from that pump is taken out, mixed, add host polymer and after this shear stage, add silica base particle before the shear stage of cleaning etc.When using, the LMW cationic organic polymer preferably was introduced in the paper stock before introducing host polymer.As selection, LMW cationic organic polymer and host polymer can be basically simultaneously, be introduced in the paper stock separately or with the form of mixture, for example as at U.S patent No.5, in 858,174 disclosed like that, this patent is here as with reference to introducing.LMW cationic organic polymer and host polymer preferably were introduced in the paper stock before introducing silica-based sols.
In a preferred embodiment of the invention, silica-based sols and particle are used as drainage and keep auxiliary agent with aforesaid at least a organic polymer and at least a aluminium compound.Aluminium compound can be used in drainage and/or the retention property that further improvement comprises the paper stock additive of silica base particle.The aluminium salt that is fit to comprises alum, aluminate, and aluminium chloride, aluminum nitrate, poly-aluminium compound, as polyaluminium chloride, poly aluminium sulfate, the poly-aluminium compound of content chlorine root and sulfate ion, poly-silicic acid-aluminum sulfate and their mixture.Poly-aluminium compound can also contain other anion, for example from the anion of phosphoric acid, organic acid such as citric acid and oxalic acid.Preferred aluminium salt comprises sodium aluminate, alum and poly-aluminium compound.Aluminium compound can add before or after the interpolation of silica base particle.As selection, perhaps in addition, aluminium compound can with silica-based sols at essentially identical time point, add simultaneously separately or with their mixture, for example resemble U.S. patent No.5,846,384 disclosed like that, this patent is here as with reference to introducing.In many cases, usually suitable is, early stage in this method for example before other additive, adds aluminium compound in paper stock.
Drainage according to the present invention and each component of keeping auxiliary agent are added in the paper stock that will dewater, its amount can be especially according to the type and the number of component, the type of batching, filer content, the type of filler, the moment of interpolation (point) etc.s are variation in the tolerance.Generally, component is to obtain than the amount interpolation of comparing more excellent drainage and/or retention when not adding these components.Silica-based sols and particle are usually with 0.001wt% at least, and the amount of 0.005wt% is added at least usually, according to SiO
2Calculate and with dry paper stock material, i.e. the optional filler of cellulose fiber peacekeeping be basic, and upper limit 1.0wt% normally, that suitable is 0.5wt%.Host polymer often be the amount interpolation of 0.005wt% at least usually with 0.001wt% at least, and based on dry paper stock material, its upper limit is 3wt% normally, and that suitable is 1.5wt%.When using the LMW cationic organic polymer in the method, it can be with the amount interpolation of 0.05wt% at least, based on the paper stock dry that will dewater.What be fit to is that this amount is in the scope of 0.07-0.5%, preferably in the scope of 0.1-0.35%.When using aluminium compound in the method, be incorporated into other effect that the total amount in the paper stock that will dewater depends on the type of used aluminium compound and wants to be obtained by it.For example, what be known in the art is to utilize the precipitating agent of aluminium compound as colophony type sizing agent (sizing agent).The total amount of adding normally at least 0.05% is according to Al
2O
3Calculate and be base with dry paper stock material.What be fit to is that this amount is in the scope of 0.1-3.0%, preferably in the scope of 0.5-2.0%.
Other additive commonly used in papermaking can be used in combination with additive according to the present invention certainly, dry strength agent for example, wet strength agent, fluorescent whitening agent, dyestuff, adhesive resembles colophony type adhesive and cellulose reactive adhesive, for example alkyl and alkenyl ketone dimer and ketone polymer, alkyl and olefin butyric anhydride etc.Cellulose suspension or paper stock also can contain the inorganic filler of general type, as kaolin, china clay, titanium dioxide, gypsum, talcum and natural and synthetic calcium carbonate such as chalk, powdery marble (ground marble) and winnofil.
Method of the present invention can be used for the production of paper.Here employed term " paper " comprises paper not only and its production method certainly, also comprises the sheet material or the paper web shape product of cellulose fiber, for example plate and cardboard, and their production method.This method can be used in from the suspension of the fiber of dissimilar cellulose and produces paper, and this suspension should suit to contain 25wt% and the preferred this fiber of 50wt% at least at least, based on dry.This suspension can be with from chemical pulp such as sulfate pulp, sulfite pulp and organosol paper pulp, mechanical pulp such as preheating mechanical pulp, chemistry-thermomechanical pulp, the fiber of refined pulp and ground wood pulp is the basis, based on fiber from hardwood and cork, and can also be based on optional from the recycled fibers of de inked pulp and their mixture.Suspension is that the pH of paper stock can be in the scope of about 3-about 10.This pH is adapted at more than 3.5 with preferably in the scope of 4-9.
In following examples, further explained the present invention, yet these embodiment are used for limiting the present invention.Part and % are respectively weight portion and wt%, unless otherwise prescribed.
Embodiment 1
Preparation standard silica sol as described below:
762.7g have a SiO of 3.3
2With Na
2O mol ratio and 27.1% SiO
2The sodium silicate of content is diluted with water to 3000g, has produced the SiO with 6.9wt%
2The silicate solutions of content (I).This silicate of 2800g or water glass solution are by a pillar that is filled with the saturated strong cation-exchanging resin of hydrogen ion.From ion-exchanger, collect the SiO of 2450g with 6.5wt%
2Ion-exchange waterglass or the poly-silicic acid (II) of content and 2.4 pH feed reactor with the poly-silicic acid (II) of 1988g, with the dilution of 12.3g water.6.9% silicate solutions (I) that under strong agitation, adds 173.9g then.Gained solution heated 60 minutes down at 85 ℃ then, was cooled to 20 ℃ then.Institute's silica sol that obtains (1a) has following characteristic:
Colloidal sol 1a (reference): SiO
2Content=7.3wt%, SiO
2/ Na
2O mol ratio=40, pH=10.2, S-value=29%, the specific area=530m of viscosity=2.2cP and particle
2/ g.
Production has two kinds of other silica sol of following characteristic, i.e. colloidal sol 1b and colloidal sol 1c:
Colloidal sol 1b (reference): SiO
2Content=7.3wt%, SiO
2/ Na
2O mol ratio=63, pH=10.0, S-value=26%, the specific area=500m of viscosity=2.7cP and particle
2/ g.
Colloidal sol 1c (reference): SiO
2Content=5.4wt%, SiO
2/ Na
2O mol ratio=35, pH=9.8, S-value=32%, the specific area=690m of viscosity=1.6cP and particle
2/ g.
Embodiment 2
(produce with the same ion switching method, have the SiO of 5.46wt% with the poly-silicic acid that is similar to poly-silicic acid (II)
2Content) prepare six kinds of colloidal sols according to silica base particle of the present invention.Under strong agitation, add 3.3 the SiO of having of 1.46kg to the poly-silicic acid of 102.0kg
2/ Na
2The sodium silicate of O ratio has produced and has had 54.0 SiO
2/ Na
2The solution of O mol ratio.This solution is cooled to 20 ℃ again 60 ℃ of following heat treatments 2 hours 20 minutes, and product is condensed to the SiO of 15.6wt% thus
2Content.This centre colloidal sol product is divided into six kinds of independent samples, i.e. a-f now.Further with the NaOH alkalization, sample d-f's sample a-c alkalizes with waterglass, to obtain SiO
2/ Na
2The O mol ratio between 21.5 and 34.0 and silica content be the colloidal sol of about 15.0wt%.The colloidal sol of the silica base particle that obtains has the characteristic of listing in table 1:
Table 1
| Colloidal sol | Mol ratio [SiO 2/Na 2O] | pH | S-value [%] | Viscosity [cP] | Specific area [m 2/g?SiO 2] |
| Colloidal sol 2a | 21.5 | 10.7 | 31 | 17 | 720 |
| Colloidal sol 2b | 28.0 | 10.3 | 30 | 29 | 710 |
| Colloidal sol 2c | 34.0 | 10.0 | 29 | 40 | 690 |
| Colloidal sol 2d | 21.5 | 10.7 | 31 | 20 | 680 |
| Colloidal sol 2e | 28.0 | 10.3 | 29 | 34 | 670 |
| Colloidal sol 2f | 33.0 | 10.0 | 29 | 38 | 680 |
Embodiment 3
With above-mentioned ion-exchange process production and as among the embodiment 2, being basified to 54.0 SiO with waterglass
2/ Na
2The poly-silicic acid (II) of O mol ratio was 60 ℃ of following heat treatments 1 hour.3.3 the SiO of having that adds 7.25kg to this product of 58kg
2/ Na
2The dilution water glass of the silica content of O mol ratio and 5.5wt%.With the colloidal sol of gained silica base particle, promptly colloidal sol 3 is condensed into the silica content of 15.2wt%, and has SiO
2/ Na
2O mol ratio=24, pH=10.7, S-value=34%, the specific area=760m of viscosity=9.0cP and particle
2/ g.
Embodiment 4
The SiO of 1000g with 5.5wt%
2The poly-silicic acid (II) of content and the SiO of 14.5g with 27.1wt%
2Content and SiO
2/ Na
2The waterglass of O mol ratio=3.3 mixes under strong agitation, has produced SiO
2/ Na
2The O mol ratio be 51 and silica content be 5.8wt%SiO
2Product, this product is concentrated to 16.7wt%SiO then 60 ℃ of following heat treatments 1.5 hours
2Silica content.The obtained product of 283g mixes with 33.0g NaOH, has produced the colloidal sol of silica base particle, and promptly colloidal sol 4, silica content=15.2wt% wherein, SiO
2/ Na
2O mol ratio=21, pH=10.6, S-value=32%, the specific area=720m of viscosity=14.2cP and particle
2/ g.
Embodiment 5
According to the general step according to embodiment 3, just heat treatment was carried out 1.25 hours, concentrated and proceeded to higher silica content.Two kinds of colloidal sols of preparation silica base particle: colloidal sol 5a and 5b.Colloidal sol 5a has SiO
2Content=18wt%, SiO
2/ Na
2O mol ratio=18, pH=10.7, S-value=36%, the specific area=700m of viscosity=18cP and particle
2/ g.Colloidal sol 5b has SiO
2Content=20wt%, SiO
2/ Na
2O mol ratio=18.3, pH=10.7, S-value=37%, the specific area=700m of viscosity=31cP and particle
2/ g.
Embodiment 6
Use available from Akribi, the dynamic drainage analyzer (DDA) of Sweden is estimated water filtering performance, measure when corkage and when applying vacuum, allow used time of paper stock drainage of setting volume through rack (wire) in a side of the opposite rack of a side that exists with paper stock.
Used paper stock is a blend of bleaching pine sulfate based on 60% bleaching betulinic acid salt and 40%, adds 30% powder lime carbonate again as filler.Stock volume is 800ml, and denseness is 0.25%, and pH about 8.0.By adding sodium sulphate the conductance of paper stock is adjusted to 0.47mS/cm.
In test, silica-based sols and cationic polymer Raisamyl 142 unite use, this polymer is to have in 0.042 substitution value common-starch of height cationization, joins in the paper stock with the amount of 12kg/ ton, calculates by the dry starch based on dried paper stock system.Silica-based sols according to embodiment 1-4 is tested in the present embodiment.In addition, colloidal sol 6a and 6b also test, with the purpose that is used to contrast.Colloidal sol 6a is purchased silica sol, S-value=45% wherein, SiO
2Content=15.0wt%, SiO
2/ Na
2O mol ratio=40, the specific area=500m of viscosity=3.0cP and particle
2/ g.Colloidal sol 6b is that another is purchased silica sol, S-value=36% wherein, SiO
2Content=10.0wt%, SiO
2/ Na
2O mol ratio=10, the specific area=880m of viscosity=2.5cP and particle
2/ g.Silica-based sols adds with the amount of 0.5kg/ ton, presses SiO
2Calculate and be base with dried paper stock system.
Paper stock speed with 1500rpm in entire test stirs in iris type jar (baffled jar), chemicals adds as described below carrying out: i) add cationic starch in paper stock, stirred for 30 seconds subsequently, ii) add silica-based sols in paper stock, stirred for 15 seconds subsequently, iii) in automatic record drainage time, allow the paper stock drainage.
The drainage time of different silica-based sols is illustrated in the table 2:
Table 2
| Silica-based sols | Dewatering time [second] |
| Colloidal sol 1a (reference) | 12.0 |
| Colloidal sol 1b (reference) | 11.1 |
| Colloidal sol 1c (reference) | 12.0 |
| Colloidal sol 2d | 9.7 |
| Colloidal sol 3 | 9.5 |
| Colloidal sol 4 | 9.4 |
| Colloidal sol 6a (reference) | 12.0 |
| Colloidal sol 6b (reference) | 9.8 |
Embodiment 7
Estimate water filtering performance according to the general step of embodiment 6, just paper stock has 0.3% denseness and about 8.5 pH.Retention property is estimated by the turbidity of the plain boiled water measuring filtrate, obtain by the paper stock drainage with nephelometer.
Silica-based sols according to the embodiment of the invention 5 compares test with colloidal sol 6a.Table 3 has been represented the drainage time that (kg/ton) obtains under the various dose of silica base particle, according to SiO
2Calculate and be base with dry paper stock system.Only add cationic starch (the 12kg/ ton calculates with the dry starch based on dried paper stock system) and obtained 15.8 seconds drainage time.
Table 3
Claims (21)
1, the hydrosol that contains silica base particle is characterised in that it has the interior S-value of 10-45% scope, viscosity in the 5-40cP scope and the SiO in the 10:1-40:1 scope
2/ M
2The O mol ratio, wherein M is alkali metal or ammonium.
2, the hydrosol that contains silica base particle is characterised in that it has S-value in the 10-45% scope, viscosity in the 5-40cP scope and the silica content of 10wt% at least.
3,, be characterised in that it has the silica content of 10wt% at least according to the hydrosol of claim 1.
4, according to claim 1,2 or 3 the hydrosol, be characterised in that silica base particle has at 775-1050m
2Specific area in the/g scope.
5, according to claim 1,2 or 3 the hydrosol, be characterised in that silica base particle has at 550-725m
2Specific area in the/g scope.
6, according to each the hydrosol of claim 1-5, be characterised in that the S-value is in the scope of 20-40%.
7, according to each the hydrosol among the claim 1-6, be characterised in that viscosity is in the scope of 7-25cP.
8,, be characterised in that it has SiO in the 15:1-30:1 scope according to each the hydrosol among the claim 1-7
2/ M
2The O mol ratio, wherein M is alkali metal or ammonium.
9,, be characterised in that it has at least 10.6 pH according to each the hydrosol among the claim 1-8.
10, be used to produce the method for silica base particle, be characterised in that it may further comprise the steps:
(a) pH that aqueous silicate solution is acidified to 1-4 to be forming acid-sol,
(b) SiO in the 4.5-8wt% scope
2Content down alkalization acid-sol is at least 7 to pH,
(c) make the germination at least 10 minutes and then of alkalization colloidal sol
(d) alkalization institute's colloidal sol that obtains arrives at least 10.0 pH.
11, be used to produce the method for silica base particle, be characterised in that it may further comprise the steps:
(a) the acidifying aqueous silicate solution to the pH of 1-4 forming acid-sol,
(b) SiO in the 4.5-8wt% scope
2Content is the alkalization acid-sol down,
(c) heat treatment alkalization colloidal sol and then under at least 30 ℃ temperature
(d) the heat treated colloidal sol of alkalization arrives at least 10.0 pH.
12,, be characterised in that according to (b) and alkalization (d) and carry out with aqueous silicate solution according to the method for claim 10 or 11.
13,, be characterised in that according to the germination of (c) and heat treatment it is to carry out under the temperature in 35-95 ℃ of scope according to claim 10,11 or 12 method.
14,, be characterised in that according to the germination and the heat treatment of (c) and carried out 20-240 minute according to claim 10,11,12 or 13 method.
15,, be characterised in that the alkalization according to (d) has produced the SiO that has in the 15:1-30:1 scope according to each method among the claim 10-14
2/ M
2O mol ratio and at least 10.6 pH, wherein M is alkali metal or ammonium.
16, by each the obtainable silica base particle of method according to claim 10-15.
17, according to claim 1-9 or 16 or by the silica base particle produced according to each method among the claim 10-15 in papermaking as drainage with keep the purposes of auxiliary agent.
18, be used for from the method for the waterborne suspension production paper that contains the optional filler of cellulose fiber peacekeeping, comprise silica base particle and at least a charged organic polymer are joined in the suspension, suspension is shaped and drainage on rack, be characterised in that silica base particle with according among the claim 1-9 each or exist by the hydrosol of producing according to each method among the claim 10-15.
19,, be characterised in that charged organic polymer is cationic starch or cationic polyacrylamide according to the method for claim 18.
20,, be characterised in that before adding to silica base particle in the suspension silica base particle dilute with water or mix the hydrosol that has the silica content of 0.05-5wt% with formation with water according to the method for claim 18 or 19.
21, according to each method among the claim 18-20, be characterised in that silica base particle joins in the suspension with the amount of 0.005-0.5wt%, presses SiO
2The filler that calculates and choose wantonly with the cellulose fiber peacekeeping is a base.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13235999P | 1999-05-04 | 1999-05-04 | |
| EP99850074 | 1999-05-04 | ||
| EP99850074.8 | 1999-05-04 | ||
| US60/132,359 | 1999-05-04 | ||
| SE9901687-5 | 1999-05-06 | ||
| SE9901687A SE9901687D0 (en) | 1999-05-06 | 1999-05-06 | Silica-based sols |
| SE99016875 | 1999-05-06 | ||
| US16244599P | 1999-10-29 | 1999-10-29 | |
| EP99850160.5 | 1999-10-29 | ||
| US60/162,445 | 1999-10-29 | ||
| EP99850160 | 1999-10-29 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008071489A Division CN100473604C (en) | 1999-05-04 | 2000-04-28 | Silica-based sols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101476262A true CN101476262A (en) | 2009-07-08 |
| CN101476262B CN101476262B (en) | 2011-08-03 |
Family
ID=37721282
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100038192A Expired - Fee Related CN101476262B (en) | 1999-05-04 | 2000-04-28 | Silica-based sols |
| CN2005101250842A Expired - Fee Related CN1912242B (en) | 1999-05-04 | 2000-04-28 | Paper making method |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005101250842A Expired - Fee Related CN1912242B (en) | 1999-05-04 | 2000-04-28 | Paper making method |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922349A (en) * | 2014-04-19 | 2014-07-16 | 济南银丰化工有限公司 | Silicasol with high freezing resistance and manufacturing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO300125B1 (en) * | 1988-03-16 | 1997-04-14 | Nissan Chemical Ind Ltd | Stable liquid silica sol, as well as process for its preparation |
| CN1029950C (en) * | 1990-11-09 | 1995-10-11 | 埃卡诺贝尔公司 | Silica sols, process for production of silica sols and use of sols |
| SE501214C2 (en) * | 1992-08-31 | 1994-12-12 | Eka Nobel Ab | Silica sol and process for making paper using the sun |
| US5477604A (en) * | 1993-11-01 | 1995-12-26 | Smith; Daniel | Process for manufacturing taper point surgical needles |
-
2000
- 2000-04-28 CN CN2009100038192A patent/CN101476262B/en not_active Expired - Fee Related
- 2000-04-28 CN CN2005101250842A patent/CN1912242B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922349A (en) * | 2014-04-19 | 2014-07-16 | 济南银丰化工有限公司 | Silicasol with high freezing resistance and manufacturing method thereof |
| CN103922349B (en) * | 2014-04-19 | 2016-02-24 | 山东银丰纳米新材料有限公司 | A kind of high anti-freezing type silicon sol and manufacture method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1912242A (en) | 2007-02-14 |
| CN1912242B (en) | 2011-01-12 |
| CN101476262B (en) | 2011-08-03 |
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