# Patent

## Title
Method for producing SiO2 granulate

## Abstract

The invention relates to a process for producing SiO2 granules by freezing and re-thawing an SiO2 suspension, wherein a separation of liquid and sediment composed of agglomerated SiO2 particles occurs in the course of thawing, the liquid removed is decanted and the residual moisture in the sediment is removed by a drying step with formation of the SiO2 granules. According to the invention, an auxiliary comprising alkali metal-free bases in the form of nitrogen hydrides is added to the suspension to set the pH greater than 7.

## Background
TECHNICAL BACKGROUND OF THE INVENTION
The present invention refers to a method for producing a SiO2 granulate, comprising providing a suspension containing SiO2 particles in an aqueous liquid, freezing the suspension and removing the liquid, wherein the frozen SiO2 suspension is thawed so as to form a liquid phase and a sediment of agglomerated SiO2 particles, the liquid phase is removed and the sediment is dried for removing residual moisture and so as to form the SiO2 granulate.
Furthermore, the present invention refers to a use of the granulate.
PRIOR ART
In ceramic process engineering, various methods are known for producing granulates which can also be used for SiO2 or other glasses. As a rule, a granular mass is produced by removing moisture from a suspension. Pressure and temperature conditions play an essential role. Furthermore, the step of removing moisture can be supported mechanically.
DE 197 29 505 A1 discloses a method for producing a SiO2 granulate, in which an aqueous SiO2 dispersion is homogenized in a stirring tank first under intensive stirring motion and then at a relatively low rotational speed a nitrogen stream which is heated to about 100° C. is acting on the SiO2 dispersion. Moisture is thereby removed and a substantially pore-free SiO2 granulate is obtained in the stirring tank. The method is long-winded and energy-intensive. Moreover, there is the risk of the input of contaminants because the granulating tool and the stirring dish are in a very intensive contact with the SiO2 dispersion throughout the granulating process.
Furthermore, U.S. Pat. No. 3,401,017 discloses SiO2 pigments which are inter alia used as fillers in rubber or plastics. These SiO2 pigments are basically produced in the method steps: freezing and thawing of a SiO2 slurry, and drying of the SiO2 sediment after removal of the liquid phase. With the method according to U.S. Pat. No. 3,401,017 the sedimentation and compaction properties of the SiO2 pigments are to be improved, whereby the drying work is reduced.
JP 02-199015 A also refers to a method in which use is made of an aqueous SiO2 slurry that is frozen and subsequently subjected to a drying step. The thawing operation, followed by sedimentation and concentration of the SiO2 particles in the thawed slurry, is carried out in a “thickener”. Drying is then carried out in a filtration drier which is backed up by a hot-air blower and a vacuum pump. At the end of the process one obtains a dry filter cake of synthetic quartz glass.
A method for producing a glass granulate by using a frozen suspension is known from DE 41 00 604 C1. In this method, finely divided glass granulate is produced in that a glass powder of a mean grain size is dispersed and comminuted in an aqueous grinding liquid by using grinding elements of glass. After separation of the grinding elements the glass slurry is deep-frozen and subsequently freeze-dried, the frozen aqueous grinding liquid being evaporated by sublimation in high vacuum. The resulting glass granulate has a mean grain size in the range of 0.5 μm to 3 μm. Smaller granulate grains are only achievable with much longer grinding periods.
Technical Objective
Starting from the said granulation method, it is therefore the object of the present invention to indicate a method for producing a SiO2 granulate which produces a fine granulate of high purity in a particularly simple and economic way.
Furthermore, it is the object of the present invention to indicate a suitable use for the granulate.
GENERAL DESCRIPTION OF THE INVENTION
The above object, starting from a method of the aforementioned type, is achieved according to the invention in that the suspension for adjusting the pH to more than 7 contains an addition of alkali-free bases in the form of nitrogen hydrides.
According to the method of the invention an aqueous SiO2 suspension, also called SiO2 slurry, is first prepared in a container, such as a plastic bottle, it is then deep-frozen and is subsequently re-thawed to room temperature. When the SiO2 suspension is produced, alkali-free bases in the form of nitrogen hydrides are added to the suspension. This additive causes an adjustment of the pH to more than 7 and has the consequence that the hydrate shell around the SiO2 particles is broken up, whereby the suspension gets stabilized and a very homogeneous slurry is maintained also for hours. In this preparation phase, no SiO2 agglomerates from the SiO2 suspension will settle on the bottom of the receptacle. During freezing and during the thawing process, respectively, the original SiO2 particles will agglomerate and settle as a fine granulate on the bottom of the container. The original suspension liquid, i.e. water with the nitrogen hydride additions, is present as a more or less clear liquid phase over the sediment consisting of agglomerated SiO2 particles. Hence, the liquid can be removed without difficulties, e.g. by decanting, suction or centrifugation. What remains as the sediment is the moist SiO2 granulate that must only be subjected to a drying step for eliminating the remaining water. The SiO2 granulate obtained with granulate particle sizes of up to about 700 μm is relatively soft and thereby easily disintegrates into finely divided granulate grains. The SiO2 granulate obtained can also be used without any further comminuting measures. It has further been found that the grain distribution of the SiO2 granulates obtained is shifted in favor of smaller grain sizes due to the addition of nitrogen hydrides to the SiO2 slurry—i.e. the coarse proportion can be minimized.
A stirring tool or another mechanical auxiliary device is not needed for granulation. Freezing and thawing of the slurry can be carried out in the same container in which the slurry formulation has been homogenized, so that the risk of contact contamination with other materials is minimized. The method according to the invention is therefore particularly suited for producing high-purity, doped and non-doped SiO2 granulates.
This procedure for producing a SiO2 granulate is simple, fast and reliable.
The remarkable phase separation in the sediment and liquid phase during thawing is presumably due to the strong volume change during the phase transition ice-water. The SiO2 slurry first represents a colloidal suspension the stability of which is achieved by way of ion occupation on the surface of the SiO2 particles. A sedimentation by allowing the aqueous SiO2 suspension to stand quiet will therefore only take place after a long time and will then normally lead to a more or less firm “SiO2 cake”, but not to a finely divided granulate. It could be imagined for the method according to the invention that the large dendritic ice crystals which are formed in the freezing process destroy the ion occupation on the surface of the SiO2 particles and thereby change the tendency to aggregation and the flow properties of the SiO2 particles, respectively. In the thawing process the SiO2 particles can then more easily separate from one another or they agglomerate together due to the considerably reduced agglomeration forces into small granulate particles that can easily sediment.
An advantageous configuration of the invention is that the water content of the suspension during freezing is at least 30% by wt. to not more than 90% by wt., preferably at least 70% by wt. This relatively great water amount ensures a good wetting of the SiO2 particles, so that the large ice crystals can exhibit their action during thawing of the suspension. Moreover, the water ensures a homogeneous slurry in the preparation of the SiO2 suspension. Since the individual SiO2 particles in the suspension with a high water content are spaced apart to a relatively great extent, the dopants can be distributed easily in a corresponding manner, thereby permitting a homogeneous doping. Moreover, a SiO2 suspension with a relatively low solids content yields a rather finely divided granulate.
Furthermore, it has turned out to be advantageous when the SiO2 suspension is frozen in a temperature range of −5° C. to −40° C. This temperature range represents a suitable compromise between productivity and energy consumption. At a temperature of only shortly below 0° C., the freezing operation for complete thorough freezing of the SiO2 suspension takes a long time and the method tends to be inefficient. Freezing temperatures of less than −40° C. are certainly possible, but the equipment needed for this is considerable without improving the efficiency of the method according to the invention. The period for freezing the suspension is preferably at least 12 hours, a duration that can be integrated into standard industrial manufacturing sequences.
By addition of nitrogen hydrides, preferably in the form of ammonia (NH3), ammonium carbonate ((NH4)2CO3), Urotropin (C6H12N4) or ammonium carbamate (CH6N2O2), the pH of the suspension can be adjusted to more than 7, preferably between 12 and 14, which has an advantageous effect on the homogeneous distribution thereof when a dopant is added. The above-mentioned auxiliaries help to break up the hydrate shell around the SiO2 particles, so that the suspension gets stabilized. When dopants are added, these can thus easily deposit on the SiO2 particles and can be distributed in the suspension.
An addition of one to two volume percent of the nitrogen hydride, preferably concentrated ammonia solution, has turned out to be useful.
It has turned out to be advantageous for the thawing process when this process is carried out in a resting suspension at an ambient temperature ranging from 20° C. to 100° C. At higher temperatures already a part of the aqueous liquid will evaporate, so that a transition phase to the drying step is initiated, which may also be advantageous in individual cases.
To accelerate the thawing process, the frozen SiO2 slurry may be acted upon with microwaves. The action of low-power microwave radiation reduces the duration for the thawing process.
If the suspension contains soluble impurities, it has turned out to be advantageous when the sediment of agglomerated SiO2 particles is washed after separation of the liquid phase by way of slurrying in demineralized water. The impurities, e.g. in the form of salts, can thereby be removed easily. This washing operation can be carried out easily because when water is poured onto the sediment a SiO2 suspension will be formed having SiO2 particles that sediment at a faster pace and form a sediment again. Thus the washing operation can be carried out within a short period of time even if repeated several times.
As for the drying process for removing the residual moisture in the sediment, it is further advantageous to select a temperature range of 100° C. to 500° C. This temperature range is covered by simple drying cabinets, so that no great efforts with respect to the equipment are needed for the drying step. In principle, it is also possible to supply the sediment consisting of agglomerated SiO2 particles to a drying segment in a continuous furnace. The temperature which is raised relative to the room temperature leads to a swift drying of the sediment and to the desired SiO2 granulate.
For a further optimization of the drying step, it has turned out to be advantageous when the sediment is moved mechanically, for instance by slightly shaking the container with the SiO2 granulate.
It may be helpful for the drying of the sediment to minimize the residual moisture by way of filtration.
To further optimize the drying process, the sediment consisting of agglomerated SiO2 particles may be centrifuged after removal of the liquid phase so as to separate further aqueous liquid. The centrifuging process shortens the drying period because the liquid contained in the sediment is expelled within a few minutes. Moreover, during the centrifuging process, very tiny suspended particles from the liquid will reliably settle, so that the separation of solid from liquid is optimized.
An advantageous variant of the invention is that the SiO2 suspension is frozen in a closed container and re-thawed. This measure prevents a possible input of impurities during the freezing and thawing phase.
Advantageously, apart from the SiO2 particles, the aqueous SiO2 suspension contains dopants.
The method according to the invention is particularly also suited for the production of doped SiO2 granulate in the case of which the demands made on the homogeneity of the dopant distribution are very high. This is in general the case with applications in the optical sector. Quartz glasses for passive optical waveguides, laser glasses and filter glasses should here be mentioned by way of example.
In this connection it has also turned out to be useful when as the dopant an oxide, or plural oxides, or a precursor thereof, such as chlorides or fluorides, is used, selected from the following group of elements: Al, B, P, Nb, Ta, Mg, Ga, Zn, Ca, Sr, Ba, Cu, Sb, Bi, Ge, Hf, Zr, Ti and all rare-earth metals.
Since the amount and homogeneous distribution of the dopants is of great importance to the said applications, it is especially the method of the invention based on frost granulation that is suited because the risk of the input of external elements, which elements might destroy the effect to the selectively used dopants, is minimized.
The SiO2 granulate obtained according to the method of the invention is distinguished by a particle size of the granulate particles in the range of less than or equal to 700 μm. These granulates are soft and decompose under only slight pressure into smaller aggregates. This may be of advantage during further processing because upon crushing of the soft granulate grains the granulate is subjected to further thorough mixing.
The SiO2 granulate produced according to the method of the invention is particularly suited as a start substance for optically active materials for laser-active components, such as fiber lasers, rod lasers or disk lasers. Furthermore, these SiO2 granulates are suited as start substance for filter glasses or for producing the synthetic inner layer in quartz glass crucibles during melting of silicon. Apart from this, the production of components from quartz glass for use in dry etching processes of the semiconductor industry should be mentioned as an application for the SiO2 granulates produced according to method according to the invention. These possibilities of use are particularly given if dopants have been added to the SiO2 suspension. The homogeneous dopant distribution is also maintained in the granulate, whereby optimal further processing possibilities are given.



EMBODIMENT
The invention shall now be explained in more detail with reference to an embodiment and the drawings, in which
FIG. 1 shows a flow diagram with method steps for explaining the production of SiO2 granulate according to the invention; and
FIG. 2 shows a sieve analysis of the SiO2 granulate produced.



EXAMPLE 1
For the production of a SiO2 granulate a suspension consisting of discrete SiO2 particles in the form of SiO2 aggregates is prepared in demineralized water in a closable plastic container, e.g. a PTFE bottle with lid. This SiO2 suspension is fed drop by drop with a concentrated ammonia solution, resulting in a pH of 9.5.
The SiO2 aggregates in the slurry have a mean particle size of about 10 μm and they consist of SiO2 primary particles with particle sizes in the range of 5 nm to 100 nm.
The solids content of the SiO2 suspension is 12% by wt. For homogenization the SiO2 suspension is thoroughly stirred for several hours, resulting in a stable homogeneous SiO2 suspension in the end. The bottle with the suspension is closed by a lid or by a suitable foil and is subsequently deep-frozen overnight in a freezer at −18° C. For thawing the container with the frozen SiO2 suspension is taken from the freezer and thawed at room temperature.
During thawing the agglomerated SiO2 particles separate as sediment from the water, so that the sediment is present in the lower half of the container and, above this sediment, the water as a more or less clear liquid.
The liquid is subsequently poured off. The residual water remaining in the sediment can be evaporated by drying the sediment at 120° C. in a drying cabinet. This drying step can be accelerated by slightly shaking e.g. the container with the moist sediment.
An alternative method for accelerating the drying process consists in putting the moist sediment of agglomerated SiO2 particles into a centrifuge. At a rotational speed of 500 rpm one obtains, depending on the weighed-in amount and the performance of the centrifuge, an almost fully dried SiO2 granulate after about 5 minutes. Unless the remaining residual moisture is even helpful in the further processing of the granulate, it can be removed by slight heating within a very short period of time.
FIG. 2 shows the result of the sieve analysis according to the method according to DIN 66165-2 of the granulate obtained thereby in comparison with the SiO2 granulate according to Comparative Example 2. The relative percentage amount M (based on the total mass in weight percent) is plotted against the grain size D in μm of the SiO2 granulates. Curve A shows the grain distribution of the SiO2 granulate produced according to the invention at a residual moisture of about 40% as compared with a SiO2 granulate which has been prepared by way of frost granulation, but without the addition of nitrogen hydrides to the initial SiO2 suspension (Curve B). It has been found that the SiO2 granulate produced according to the invention has a great fraction of grain sizes in the range of 300 μm to 600μ, whereas the SiO2 granulate produced without addition of a nitrogen hydride to the SiO2 slurry has a very great coarse fraction of granulates of more than 800 μm.
The addition of nitrogen hydrides to the SiO2 slurry has then an impact on the grain distribution of the resulting SiO2 granulates in favor of smaller grain sizes, thereby reducing the prevailing coarse fraction. The grain size distribution is on the whole broader and more homogeneous. This confirms that the method according to the invention is suited for providing particularly finely divided SiO2 granulates.
The SiO2 granulate produced according to the invention is suited for use in the manufacture of high-purity quartz glass.
EXAMPLE 2
Starting from the aqueous SiO2 suspension of Example 1 this slurry is adjusted to a pH of 9.5 by adding a concentrated ammonia solution drop by drop. Thereafter, the homogenized alkaline SiO2 suspension is fed under constant stirring with dopants in dissolved form and by way of time-controlled dropwise addition of an aqueous dopant solution consisting of AlCl3 and YbCl3.
As described in Example 1, this slurry that is now doped is subsequently frozen and re-thawed. In this case, too, the solid forms a sediment during thawing, and the ammoniacal liquid is positioned thereabove, which liquid will be decanted. The sediment contains ammonium chloride (NH4Cl) from the reaction of the ammonia with the dopants. The ammonium chloride can either be sublimed at correspondingly high drying temperatures or washed out. For the washing operation, demineralized water is put on the sediment, the wet granulate settles again as sediment after a short period of time and the dissolved ammonium salts are removed by pouring off the supernatant liquid. After the initial freezing and thawing process the SiO2 particles, no matter whether they are doped or undoped, show a strong tendency to sedimentation, so that this washing operation can be repeated several times in case of need and is not time-consuming.
The granulate obtained thereby is particularly suited for the further processing into components of optically active materials for laser-active components, such as e.g. fiber lasers or for producing quartz glass for use in dry etching processes.
Comparative Example 1
A SiO2 suspension according to Example 1 is not frozen, but left to stand in a resting position for several days. There is no separation of SiO2 particles and aqueous liquid. For the removal of the water the slurry is dried in a drying cabinet at 120° C. for 24 hours.
What remains is a firm “SiO2 cake” which is ground with a mortar by hand into a coarse splintery granulate. Moreover, due to treatment with the mortar there is an increased risk of the input of contaminants into the SiO2 granulate.
Comparative Example 2
An aqueous SiO2 suspension of discrete SiO2 particles in the form of SiO2 aggregates is produced in demineralized water in a closable plastic container, e.g. a PTFE bottle with lid. Subsequently, the SiO2 suspension is frozen in a freezer without addition of a nitrogen hydride. During thawing at room temperature the agglomerated SiO2 particles separate as sediment from the water, so that the sediment is present in the lower half of the container and, above this sediment, the water as a more or less clear liquid.
The liquid is subsequently poured off. The residual water remaining in the sediment can be evaporated by drying the sediment at 120° C. in a drying cabinet.
The SiO2 slurry without addition of nitrogen hydrides yields a relatively hard SiO2 granulate which is partly also present in small lumps. The grain analysis according to FIG. 2, Curve B, shows a great coarse fraction of up to 65% for grain sizes between about 800 μm and >1000 μm in comparison with granulates the starting material of which was a SiO2 slurry with addition of ammonia as nitrogen hydride (FIG. 2 Curve A).

## Claims

1. A method for producing a SiO2 granulate, said method comprising:
providing a suspension containing SiO2 particles in an aqueous liquid,
freezing the suspension and removing the liquid, including thawing the frozen SiO2 suspension so as to form a liquid phase and a sediment of agglomerated SiO2 particles,
removing the liquid phase and drying the sediment so as to remove residual moisture and so as to form the SiO2 granulate,
wherein the suspension contains an addition of nitrogen hydrides such that the suspension has a pH more than 7, and
wherein the suspension is frozen for a period of at least 12 hours.

2. The process according to claim 1, wherein the water content of the suspension during freezing is at least 30% by wt. and not more than 90% by wt.

3. The process according to claim 1, wherein the SiO2 suspension is frozen in a temperature range of −5° C. to −40° C.

4. A process comprising:
producing a SiO2 granulate according to a method comprising:
providing a suspension containing SiO2 particles in an aqueous liquid,
freezing the suspension and removing the liquid, including thawing the frozen SiO2 suspension so as to form a liquid phase and a sediment of agglomerated SiO2 particles,
removing the liquid phase and drying the sediment so as to remove residual moisture and so as to form the SiO2 granulate,
wherein the suspension contains an addition of nitrogen hydrides such that the suspension has a pH more than 7, and
wherein, apart from SiO2 particles, the aqueous SiO2 suspension also contains dopants, and the dopants include
an oxide, oxides, or a precursor of an oxide or oxides, of Al, and
an oxide, oxides, or a precursor of an oxide or oxides, of one of the rare-earth metals; and
using the SiO2 granulate as a starting material for an optically active material for laser-active component.

5. The process according to claim 4, wherein ammonia (NH3) or ammonium carbonate ((NH4)2CO3) or Urotropin (C6H12N4) or ammonium carbamate (CH6N2O) is added as nitrogen hydride.

6. The process according to claim 4, wherein nitrogen hydride is added to the aqueous liquid in such an amount that a pH of the suspension is in the range of 9.5 to 14.

7. The process according to claim 4, wherein after the removing of the liquid phase the sediment of agglomerated SiO2 particles is washed by being slurried in demineralized water.

8. The process according to claim 4, wherein the drying step of the sediment is carried out in a temperature range of 100° C. to 500° C.

9. The process according to claim 4, wherein the sediment is moved while being dried.

10. The process according to claim 4, wherein the removing of the liquid phase comprises decanting and subsequent centrifuging of the sediment of agglomerated SiO2 particles so as to produce separation of further aqueous liquid.

11. The process according to claim 4, wherein the SiO2 suspension is frozen in a closed container.

12. The process according to claim 4, wherein the SiO2 granulate is of granulate particles having a particle size up to 500 μm.

13. The process according to claim 4, wherein the water content of the suspension during freezing is at least 70% by wt and not more than 90% by wt.

14. The process according to claim 4, wherein nitrogen hydride is added to the aqueous liquid in such an amount that the pH of the suspension is more than 12.

15. The process according to claim 4, wherein the suspension is frozen for a period of at least 12 hours.

16. The process according to claim 4, wherein the water content of the suspension during freezing is at least 30% by wt. and not more than 90% by wt.

17. The process according to claim 4, wherein the SiO2 suspension is frozen in a temperature range of −5° C. to −40° C.