Patent Application
20190161355
The invention relates to a process for production of silica having variable thickening wherein the feedstocks are mixed by static mixing elements before entry into a reaction chamber.
Processes for producing pyrogenous silicas with high thickening are known. DE-A-2609487 discloses a process wherein pyrogenically formed silica is treated with silicon tetrachloride in a subsequent step and then hydrolysed and deacidified with an air/steam mixture.
DE-A-2904199 proposes a process which comprises a step of introducing into the reaction mixture additional amounts of steam which do not result from the combustion of gases comprising hydrogen needed for the flame hydrolysis.
EP-A-38900 recites a process for production of pyrogenous silica with high thickening wherein siloxanes are converted in the presence of hydrogen and air.
EP-A-97378 discloses a process for adjusting the thickening wherein the pyrolysis flame is supplied with additional energy, for example in the form of a combustible gas.
EP-A-634360 discloses a process wherein gas discharges are produced in the combustion chamber by means of a gas gun.
WO2006/087136 states that high-thickening silicas are obtainable by establishing conditions leading to a highly uniform, radial distribution of temperatures without further specifying these conditions.
Existing solutions for producing high-thickening pyrogenous silica either proceed from costly feedstocks or require costly changes to the equipment. The problem addressed by the present invention was therefore that of providing a process making it possible to provide silica having variable thickening in a simple and economical manner at low equipment-related costs.
The invention accordingly provides a process for production of silica having variable thickening wherein
Hydrolysable for the purposes of the invention is to be understood as meaning that the silicon compound in the presence of steam are transformed into silica and a byproduct which is gaseous under the reaction conditions. Examples thereof are:
SiCl4+2H2O→SiO2+4HCl; Si(OEt)4+2H2O→SiO2+4EtOH.
Oxidizable for the purposes of the invention is to be understood as meaning that the silicon compound in the presence of oxygen are converted into silica and a gaseous byproduct. An example thereof is: SiCl4+O2→SiO2+2Cl2.
In the context of the invention, volumes and velocities are specified in standardized form. Nm3 represents a volume at a pressure of 1.01325 bar and a temperature of 0° C. Nm/s represents a standardized velocity calculated from the volume and a cross section.
Pipepieces A and/or B comprising the static mixing elements are static mixers where through the product streams to be mixed flow. They cause the formation of secondary flows extending across relatively large regions. Turbulent regions are also formed and lead to finer mixing. In principle, the choice of static mixer is not subject to any limitation. Examples of static mixers useful in the present invention are found for example in U.S. Pat. Nos. 4,758,098 or 5,522,661. And pipepieces A and B comprising the static mixing elements can be the same or different as regards their dimensions and the nature of the mixing elements.
Preferably, however, the process according to the invention utilizes flange mixers wherein mixing operations take place downstream of the static mixing elements. A flange mixer of this type is disclosed for example in U.S. Pat. No. 5,839,828 wherein the reaction stream to be introduced is fed via one or more diaphragms.
In EP-A-1153650 the reaction stream to be introduced is imported via ring metering means having a special vane arrangement.
It is particularly preferable for pipepieces A and/or B to be configured in the form of flange mixers as disclosed in EP-A-1302236. These have the vane arrangement disclosed in EP-A-1153650, but a single punctiform feed port is provided instead of the ring metering means.
Very particular preference is given to an embodiment utilizing the static mixer disclosed in EP-A-1493485. In this static mixer, internals arranged in a pipepiece comprise flat, folded or curved obstacles to flow and also constrictions therebetween, wherein the primary obstacles to flow are geometrically modified on their surfaces and/or at their edges, and these modifications are capable of inducing local streams of second order in a first product stream which superimpose on the flow of first order and thereby improve the quality of mixing in that radial and axial inhomogeneities in the fluid are rectified more effectively than by the flow of first order. The static mixer contains a feed port for a further product stream whereby said further product stream is introduced into a zone of the mixing region of the first product stream where the effect which the geometric modifications have on the flow is particularly pronounced. Explicit reference is made to FIG. 1 in EP-A-1493485.
In one particular embodiment of the invention, LA/DA is =2-20, where LA is length of pipepiece A and DA is the internal diameter of pipepiece A. Particular preference is given to an embodiment wherein LA/DA is =3-6.
In one further particular embodiment of the invention, LB/DB is =2-20, where LB is length of pipepiece B and DB is the internal diameter of pipepiece B. Particular preference is given to an embodiment wherein LB/DB is =3-6.
I-VII=product streams;
In the process according to the invention, the velocity vB at which product stream III is imported into product stream IV is greater than the velocity vA of product stream IV at the time of importation of product stream III. Preference is given to an embodiment wherein vB/vA≥4. The velocity of product stream I and of product stream II is not critical as long as care is taken to ensure that product stream I remains in the vaporous state. The measures for this are known to a person skilled in the art. A general rule for the present invention is that the velocity of the product stream imported via the feed port of pipepiece A should be at least double the velocity of the other product stream.
vA is preferably at least 15 Nm/s. A range from 20 to 100 Nm/s has proved particularly suitable. vB is preferably at least 50 Nm/s. Particular preference is given to 100≤vB≤1500 Nm/s. To produce high-thickening silica, the process according to the invention is preferably carried out as an embodiment wherein hydrogen is used as combustible gas and 100≤vB≤1500 Nm/s and 20≤vA≤50 Nm/s. The stated velocities are standardized velocities. vA is the result of dividing the volume flow in Nm3/h by the cross-sectional area of pipepiece A. vB is the result of dividing the volume flow in Nm3/h by the cross-sectional area of the feed port.
It is known from the prior art that enhanced thickening can be achieved by increasing the imported quantity of combustible gas. It has now been found that thickening can be varied solely by varying the velocities vB at constant vA. An increase in vB, i.e. the velocity at which the combustible gas stream is imported into the product stream comprising the silicon compound and the molecular oxygen can lead to enhanced thickening.
In principle, the process is not limited to the production of particular silicas. It is preferably suitable for production of silicas having a BET surface area of 50-500 m2/g, more preferably 100-400 m2/g, even more preferably 150-350 m2/g and especially 180-280 m2/g.
Variable thickening is to be understood as meaning that for substantially the same BET surface area it is possible to obtain silicas differing in thickening effect. Substantially the same BET surface area is any one specified BET surface area ±25 m2/g, generally ±15 m2/g. This means, for example, that silicas are obtainable with a BET surface area of 200±10 m2/g and a thickening effect of 3000-3700 mPas.
It is similarly possible to obtain silicas having substantially the same thickening effect coupled with significantly differing BET surface area. This means, for example, that silicas having a thickening effect of 3500±100 mPas are obtainable with a BET surface area of 110±10 m2/g and 200±10 m2/g.
Thickening, in mPas, is determined in a dispersion of a silica in an unsaturated polyester resin having a viscosity of 1300±100 mPas at a temperature of 22° C. and measured with a rotary viscometer at a shear rate of 2.7 s and a temperature of 25° C. Suitable unsaturated polyester resins comprise cocondensates of ortho- and meta-phthalic acid and maleic or fumaric acid, or anhydrides thereof, and a low molecular weight diol, for example ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,3- or 1,4-butanediol or neo-pentyl glycol ((CH3)2C(CH2OH)2), or polyols, such as pentaerythritol, preferably dissolved at 30 to 80 wt %, preferably 60 to 70 wt %, in an olefinic reactive diluent as solvent, for example monostyrene. The viscosity of the polyester resin is 1300+/−100 mPas at a temperature of 22° C. 7.5 g of silica are imported into 142.5 g of polyester resin at a temperature of 22° C. and dispersed therein with a dissolver at 3000 min−1. 60 g of this dispersion are admixed with a further 90 g of the unsaturated polyester resin and dispersal is repeated. An example of a useful unsaturated polyester resin is Ludopal® P6, BASF.
In general, the process according to the invention is carried out such that the amount of oxygen is at least sufficient to convert the silicon compound and the combustible gas. In this case, lambda is not less than 1. Lambda describes the ratio of feed oxygen to stoichiometrically needed oxygen. The stoichiometrically needed amount of oxygen when the reaction of silicon tetrachloride and hydrogen as combustible gas is used as an example is attributable to the two reaction equations
2H2+O2->2H2O and SiCl4+2H2O->SiO2+4HCl.
When other combustible gases and silicon compounds are used, corresponding equations must be drawn up. Gamma describes the ratio of feed hydrogen to stoichiometrically needed hydrogen.
Product stream I according to the present invention comprises at least a vaporous, hydrolysable and/or oxidizable silicon compound. Said product stream generally further comprises a carrier gas, for example air or an inert gas such as nitrogen. The vaporous, hydrolysable and/or oxidizable silicon compound used may be with particular preference SiCl4, CH3SiCl3, (CH3)2SiCl2, (CH3)3SiCl, (CH3)4Si, HSiCl3, (CH3)2HSiCl, CH3CH2CH2SiCl3, Si(OC2H5)4, Si(OCH3)4, or mixtures thereof.
Preference is given to using SiCl4 alone or as constituent of mixtures. Suitable mixtures are in particular mixtures which in addition to SiCl4 further comprise (CH3)3SiCl and/or HSiCl3. It is immaterial in this connection whether SiCl4 is the main or a secondary component in these mixtures. Mixtures can for instance be used which in addition to SiCl4 comprise 70 wt % or more of CH3SiCl3 or 10 wt % or more of HSiCl3
In one particular embodiment of the invention, the vaporous, hydrolysable and/or oxidizable silicon compound comprises the secondary product generated in the production of polycrystalline silicon from HSiCl3 and comprising 60-99 wt % of SiCl4 and 0.5-40% of HSiCl3 as main constituents and H2SiCl2, SiH4 and H3SiCl and HCl as secondary constituents at less than 5 wt %, each based on the secondary product.
Product stream II comprises oxygen. This will generally be air or oxygen-enriched air.
Product stream III comprises or consists essentially of one or more combustible gases. These are preferably selected from the group consisting of hydrogen, methane, ethane and/or propane. Hydrogen is particularly preferred.
Product stream IV comprises the vaporous, hydrolysable and/or oxidizable silicon compound and oxygen.
Product stream V comprises the vaporous, hydrolysable and/or oxidizable silicon compound, oxygen and combustible gas.
Product stream VI is optional and can be used to import oxygen, combustible gas and/or steam into the reaction chamber. This can be used to influence the flame and if necessary stabilize it.
Product stream VII comprises at least the reaction products silica and water. Depending on the structure of the silicon compounds used and of the combustible gas, carbon dioxide and hydrochloric acid may also be present.
In a further possible embodiment of the process according to the invention, the reaction mixture leaves the reaction chamber and is then cooled, preferably to temperatures of 80 to 250° C., and subsequently treated with steam, preferably at temperatures of 350 to 750° C., before the solid material is separated off.
CompaX mixers from Sulzer are used as pipepieces A and B comprising static mixing elements.
Product stream I consists of 8 kg/h of vaporous silicon tetrachloride, has a velocity vI of 1.9 Nm/s and is mixed via the punctiform feed port, 3 mm in diameter, of a CompaX mixer A with LA/DA=5 into a product stream II, which consists of 11.9 Nm3/h air and has a velocity vII of 467.6 Nm/s. The velocity vA of resultant product stream IV is 23.4 Nm/s. A CompaX mixer B, which has the dimensions LB/DB=5 and whose punctiform feed port has a diameter of 1 mm, is used to import a product stream III in the form of 3.9 Nm3/h hydrogen into said product stream IV. The speed vB at which product stream III leaves the punctiform feed port is 1379.3 Nm/s. The way the feedstocks are added is shown in
The silica has a BET surface area of 186 m2/g and a thickening effect of 3550 mPas at 22° C.
Examples 2 to 8 are carried out in a similar manner, the operational settings are reported in the table. It is evident that the different diameters of the feed port of Compax mixer B and the associated velocities vB produce for the same dimensions LA, DA, LB and DB and substantially the same vA, silicas having substantially the same BET surface area, 186 to 218 m2/g, and significantly differing thickening, 3575 to 4250 mPas.
Example 9 is a repeat of Example 1 except that product stream II is introduced into product stream I via the punctiform feed port of CompaX mixer A. LA/DA is further=3. The way the feedstocks are added is shown in
Examples 10 and 11 have the same operational parameters as Example 9 except that the length of pipepiece A comprising static mixing elements was varied. LA/DA is 3 in Example 9, 6 in Example 10 and 15 in Example 11. While there is substantially the same BET surface area for the silicas obtained, thickening varies distinctly, from 3085 to 3495 mPas.
A mixture of methyltrichlorosilane and silicon tetrachloride is used in Example 12. For substantially the same BET surface area as in Examples 1 to 11, the silica obtained has very low thickening.
a)75:25 parts by weight CH3SiCl3/SiCl4;
b)diameter of hole for feed port of product stream II into product stream I: 3 mm;
c)Diameter of feed port of product stream V in reaction chamber: 15 mm;
d)gamma equals 1.9 in all examples;
e)velocity of feed into reaction chamber
| Number | Date | Country | Kind |
|---|---|---|---|
| 13176112.4 | Jul 2013 | EP | regional |
This application is a continuation application from U.S. application Ser. No. 14/888,610, filed on Nov. 2, 2015, which is a national stage patent application of international patent application PCT/EP2014/062356, filed on Jun. 13, 2014, the text of which is incorporated by reference, and claims the benefit of foreign priority to EP 13176112.4, filed on Jul. 11, 2013, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14888610 | Nov 2015 | US |
| Child | 16263079 | US |
