FI95922B - Stable aqueous silica suspension - Google Patents

Abstract

The invention relates to a stable and pumpable aqueous suspension of silica. This suspension is characterised in that it comprises: - a precipitated silica, - a bioresin, - a cationic surfactant chosen from the group of quaternary ammonium compounds and of sulphonium or phosphonium compounds. This suspension may be employed more particularly in papermaking.

Description

95922

Stable aqueous silica suspension

The present invention relates to stable aqueous suspensions of silica and their use in the paper industry.

Aqueous suspensions or bran of silica are used in many fields, especially in the paper industry for coating paper.

These suspensions tend to sediment or gel, making them difficult to transport or store. In fact, often during transport or after longer or shorter storage, the formation of a gel or hard pigment layer is observed under a liquid but low dry matter shell. In addition, it is often impossible to suspend silica or to obtain a slurry with a low enough viscosity to be suitable for pumping and thus for industrial use. This is a clear problem and occurs especially when trying to prepare suspensions with higher dry matter contents.

French patent application 2414387 and European patent application 194116 disclose methods for stabilizing pitchforks using xanthan gum or quaternary ammonium. These patent applications relate in particular to silica gel gels; the concentration of suspensions based on silica precipitation stabilized by these methods does not exceed the order of 10%.

The main object of the invention is therefore to provide a silica suspension which is stable, non-gelling, pumpable and dispersible after several days of storage in concentrated form.

The stable aqueous silica suspension according to the invention is characterized in that it contains 2,959,222 doped silica particles, a stabilizing biocoum which is a high molecular weight heteropolysaccharide obtained by fermentation of a carbohydrate with a microorganism, a p-cation selected from quaternary ammonium compounds or sulfonium or phosphonium compounds, and optionally aluminum or an aluminum compound.

It has been found that during storage from several days to several months, the suspensions according to the invention did not or only very little sediment and in any case retained a suitable viscosity.

Other features and advantages of the invention will become apparent from the following description of the invention and the specific, but non-limiting, examples.

The suspension according to the invention is based on silica particles obtained by precipitation. Here, silica obtained by the reaction of silicate and acid is used. The method of preparing the silicate can be any (addition of acid on top of the silicate in the vessel, total or partial simultaneous addition of acid and silicate to the vessel in water or silicate solution, etc.) and is selected based on the method of preparation of the desired type of silica suspension. The precipitated silicas which form the suspensions according to the invention are separated into gels according to the usual criteria and which are characterized in particular by the fact that the precipitated silicas have a highly dispersed pore distribution due to the discontinuous structure; gels, in turn, have a continuous three-dimensional structure. The pH of the precipitated silicas is usually neutral or basic, and the pH of the gels is usually acidic or highly acidic.

As examples of the invention, silicas which, once dried, have the standard NFX 11-622 (3.3)

II

The BET surface according to 3,95922 is generally at least 400 m2 / g and preferably between 20-400 m2 / g and more specifically between 50-250 m2 / g. The silicates may also contain oil hardeners according to NFT 30-022 (Mars 53) using dioctyl phthalate in the range of 50-400 cm 3/100 g.

The silica suspension according to the invention can be obtained by suspending pre-prepared and optionally dried silica in water.

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According to a variant of the invention, it is possible to prepare a silica suspension from the filtrate cake obtained in the precipitation reaction.

That is, the silica is precipitated, the reaction mixture is filtered, and a filter cake is obtained, which is washed if necessary. This cake is broken, forming a suspension.

According to the invention, these suspensions can be stabilized by the system described below.

This system is primarily based on bio-rubber. Biocarbons are polysaccharides with a high molecular weight, usually over one million, obtained by fermentation of carbon-25 hydrate, which is affected by the microorganism.

Among the bio-rubbers that can be used in the suspensions of the present invention, those obtained by fermentation of bacteria or fungi belonging to the genus Xanthomonas, such as Xanthomonas begoniae, Xanthomonas campestris, Xanthomonas carotae, Xanthomonas hederae, Xanthomonas, Xanthomonas malvacearum, Xanthomonas pa-pavericola, Xanthomonas phaseoli, Xanthomonas pisi, Xanthomonas vasculorum, Xanthomonas vesicatoria, Xanthomonas vi-35 tians, Xanthomonas pelargonii or Arthrobacter or Arthrobilis stabus, and in particular Arthrobacter stabus Azotobacter indicus or the genus Agrobacter and 4 95922 in particular Agrobacterium radiobacter, Agrobacterium rhizogenes, Agrobacterium tumefaciens or Alcaligenes and in particular Alcaligenes faecalis or Rhizobium or Sclerotium and in particular Sclerotium rolfi nicum or the genus Corticium or the genus Sclerotinia or the genus Stromatinia.

In particular, the gum obtained by fermentation of the Xanthomonas bacterial genus 10 is used as the bio-gum prepared by the microorganisms described above.

The invention does not, of course, depart from the use of a mixture of bio-rubbers as a stabilizing agent.

The stabilization system of the invention further comprises a cationic surfactant selected from the group consisting of quaternary ammonium compounds or phosphonium and sulfonium compounds.

The quaternary ammonium compounds can be selected from the compounds of the following Form 1: one of the aforementioned radicals should preferably have six or more carbon atoms.

Heterocyclic quaternary ammonium compounds can also be used, in which case the nitrogen atom belongs to the heterocyclic moiety and this heterocyclic moiety may be saturated or unsaturated. An example is the following format: - R5 \ x-

40 L

5,95922 wherein X is an anion and R 5 is an alkyl radical preferably having more than 7 carbon atoms; the heterocyclic moiety may be substituted.

5 As quaternary ammonium compounds, halides (especially chloride and bromide), sulphate or ammonium acetate are used in particular.

In particular, compounds of the following form can be used: R 1 N (CH 3) 3 + X, where X = Cl or Br and R e is an alkyl radical having at least 8 carbon atoms, such as cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide or hexadecimal-kyylitrimetyyliammoniumkloridi.

Among the heterocyclic compounds, mention may be made of cetylpyrrolidine chloride or bromide.

In addition, in the present invention, it is possible to use a stabilizing system further comprising aluminum or an aluminum compound. According to a particular embodiment of the invention, aluminum is used in the form of sodium aluminate or aluminum sulphate. In any case, without departing from the invention, any aluminum compound which fulfills the same function without altering the properties of silica, such as, for example, aluminum chloride, acetate, phosphate and nitrate, and alkaline and alkaline earth aluminates, can also be used.

Aluminum or an aluminum compound can be added in the production of silica, i.e. during or after precipitation. However, it is recommended to add it to the filter cake or when breaking the cake.

6 95922

Aluminum or an aluminum compound gives the suspensions a lower viscosity.

In addition, with the above-mentioned parts of the stabilizing system, it is useful to use an antibacterial agent such as formaldehyde, glutaraldehyde, sodium benzoate or sodium isotate.

The amount of biocarbon is usually between 0.05 and 1% by weight and in particular between 0.1 and 0.5% by weight relative to anhydrous silica. The amount of cationic surfactant varies mainly between 0.05 and 0.5% by weight.

When aluminum or an aluminum compound is used, the aluminum-15 content, expressed as the weight ratio of aluminum to anhydrous silica, is usually between 500 and 10,000 ppm and in particular between 1000 and 6000 ppm.

In addition, according to another particular embodiment of the invention, the silica is ground. Grinding is done to necessarily obtain a finer product with a smaller grain size distribution.

The grinding takes place in such a way as to obtain, for example, silica having an average particle diameter of between 0.5 and 15 [mu] m and in particular between 1 and 5 [mu] m (definition of the Coulter meter).

Grinding has been estimated to increase stability during the frying stage 30.

The method of preparation of the suspension is not critical. Typically, the silica is mixed in a pool as a suspension with a cationic surfactant and optionally aluminum or an aluminum compound. The bio-rubber is then added. Finally, the mixture thus obtained is ground, if necessary.

7 95922

The final pH of the suspension does not appear to be critical. In practice, it is between 5.5 and 8.5.

The dry matter content is usually at least 15% and mie-5 read more than 25%. According to the invention, it is possible in practice to obtain suspensions containing at least 35% of silica.

In addition, stable suspensions prepared as described can be used in the paper and board industry, for example, in coating, in the manufacture of specialty papers, in inkjet, in heat transfer, and in the manufacture of low basis weight papers.

Naturally, the suspensions according to the invention are suitable for known applications for this type of product, such as acting as abrasives, as an additive in concrete building materials, as additives in paints, inks, adhesives, etc.

Here are some concrete examples.

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Example 1 Starting from a powdered silica precipitate with a BET surface area of 250 m 2 / g, an oil binding of DOP of 130 cm 3/100 g and an annealing loss of 11% at 900 ° C.

90 g of this silica are dissolved in 142 g of water. 5 g of 2.5% CTAB and then 10 g of 2% Rhodopol 50 MC are added to the dispersion. The suspension has a dry matter content of 34% and a pH of 7.2. The average diameter of the suspension particles 3 0 is 20 μπι.

After six months of storage, the sedimentation volume (fixed amount / total amount) is zero. The viscosity measured at 1000 s '' with a Rheomat 115 viscimeter is 130 mPas. 35

Example 2 Silica having the same properties as in Example 1 is used, but in the form of a filter cake, the cake being obtained as a direct result of a precipitation reaction. In addition, during the production of this silica, aluminum in the form of sodium aluminate has been added in the precipitation, expressed as the ratio of aluminum to anhydrous silica.

To 6000 g of this washed cake containing 37% SiO 2 is added 117 g of 2.5% CTAB as solvent. After stirring for 15 minutes, 234 g of 2% Rhodopol 50 MC are finally added.

10

The pumped mixture is ground with a Dyno device to obtain the desired grain size.

This gives a slurry with a pH of 6.8 and containing 36% of silica in the form of particles with an average diameter of 2.9 μπι as determined by a Coulter meter.

After 60 days, the sedimentation volume is zero. The viscosity measured at 1000 s' with a Rheomat 115 viscometer is 480 mPas. The suspension is fluid and pumpable.

Example 3 A silica filter cake having a Bet surface area of 100 m 2 / g, once dried, binding to oil 25 DOP 120 ml / 100 g and an annealing loss of 10% at 900 ° C are started.

227 g of this cake (100 g of SiO 2) are broken and 48 g of water in an Ultra-Turax are added and then 10 g of 2% Rhodopol 50 MC are added. A broth with a pH of 7.5 and a silica content of 35% is obtained.

After eight days, hard sediment formation is observed. The sedimentation volume is 80%.

35 Example 4 Starting from a silica cake similar to Example 3.

I) 9 95922 253 g of this cake (100 g of SiO 2) are broken in an Ultra-Turax and 10 g of water and 8 g of a 2.5% CTAB solution are added. Stirring is continued until complete homogenization. A suspension with a pH of 6.8 and a silica content of 37% is obtained.

After one month, the viscosity of the mixture is very high, 2200 mPas measured with a Rheomat 115 viscometer in 1000 soils, making the mixture not pumpable.

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Of course, embodiments of the invention are not limited, although not all of them have been described by way of example. In particular, it includes all methods consisting of means as described, as well as combinations thereof, if used in the field of the invention, as set out in the claims.

Claims (8)

10 95922 1. A stable aqueous silica suspension, characterized in that it contains precipitated silica particles, 5. a stabilizing biocoum which is a high molecular weight heteropolysaccharide obtained by fermentation of a carbohydrate with the aid of a microorganism, a cationic surfactant selected from a quaternary surfactant selected from sulfonium or fossil phonium compounds, and optionally aluminum or aluminum compound. Suspension according to Claim 1, characterized in that the silica is obtained by decomposing the filter cake formed in the precipitation reaction. Suspension according to Claim 1 or 2, characterized in that it contains bio-gum obtained by fermentation of a carbohydrate with bacteria or fungi belonging to the genera Xanthomonas, Arthrobacter, Erwinia, Azotobacter, Agrobacter, Rhizobium, Sclerotium, Corticium, Sclerotinia or Stromatinia. Suspension according to Claim 3, characterized in that it contains xanthan gum. Suspension according to any one of the preceding claims, characterized in that it contains ammonium halide, ammonium sulphate or ammonium acetate as the quaternary ammonium compound. Suspension according to any one of the preceding claims, characterized in that it contains a heterocyclic quaternary ammonium compound. 35 Suspension according to any one of the preceding claims, characterized in that it contains, as quaternary ammonium compound, a compound of the form R 6 N (CH 3) 3 + X · in which I 95922 X = Cl or Br and R 6 is an alkyl radical having at least 8 carbon atoms. Use of suspensions according to any one of the preceding claims in the manufacture of papers and paperboards.