Hollow glass microspheres and method for producing the same

Abstract

A method for producing hollow glass microspheres includes preparing an aqueous suspension of starting materials including finely ground glass and waterglass. Combustible particles are produced from the suspension and are mixed with an AlO(OH)-containing pulverulent release agent. The mixture of combustible particles and release agent is introduced into a combustion chamber of a furnace where it is expanded at a combustion temperature which exceeds the softening temperature of the finely ground glass, to form the hollow microspheres. Hollow glass microspheres produced according to the method are also provided.

Claims

1. A method for producing hollow glass microspheres, the method comprising the following steps: preparing an aqueous suspension of starting materials including ground glass and waterglass; producing combustible particles from the aqueous suspension; mixing the combustible particles with a pulverulent release agent containing AlO(OH); introducing the mixture of combustible particles and pulverulent release agent into a combustion chamber of a furnace; and expanding the combustible particles in the combustion chamber at a combustion temperature exceeding a softening temperature of the ground glass, to form the hollow microspheres.

2. The method according to claim 1, wherein the pulverulent release agent further comprises Al(OH).sub.3.

3. The method according to claim 2, wherein: a fraction of Al(OH).sub.3 in the mixture of combustible particles and pulverulent release agent is between 6 wt % and 30 wt %; and a fraction of AlO(OH) in the mixture of combustible particles and pulverulent release agent is between 1 wt % and 25 wt %.

4. The method according to claim 2, wherein: a fraction of Al(OH).sub.3 in the mixture of combustible particles and pulverulent release agent is between 8 wt % and 25 wt %; and a fraction of AlO(OH) in the mixture of combustible particles and pulverulent release agent is between 2 wt % and 12 wt %.

5. The method according to claim 2, wherein: a fraction of Al(OH).sub.3 in the mixture of combustible particles and pulverulent release agent is between 8 wt % and 25 wt %; and a fraction of AlO(OH) in the mixture of combustible particles and pulverulent release agent is between 4 wt % and 10 wt %.

6. The method according to claim 2, wherein the pulverulent release agent further contains dehydroxylated kaolin.

7. The method according to claim 3, wherein the pulverulent release agent further contains dehydroxylated kaolin.

8. The method according to claim 4, wherein the pulverulent release agent further contains dehydroxylated kaolin.

9. The method according to claim 5, wherein the pulverulent release agent further contains dehydroxylated kaolin.

10. The method according to claim 6, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 3 wt % and 10 wt %.

11. The method according to claim 7, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 3 wt % and 10 wt %.

12. The method according to claim 8, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 3 wt % and 10 wt %.

13. The method according to claim 9, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 3 wt % and 10 wt %.

14. The method according to claim 6, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 4 wt % and 7 wt %.

15. The method according to claim 7, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 4 wt % and 7 wt %.

16. The method according to claim 8, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 4 wt % and 7 wt %.

17. The method according to claim 9, wherein the fraction of dehydroxylated kaolin in the mixture of combustible particles and pulverulent release agent is between 4 wt % and 7 wt %.

18. The method according to claim 1, wherein at least 90% of Al(OH).sub.3 particles in the pulverulent release agent have a particle diameter of less than 4 micrometers.

19. The method according to claim 1, wherein at least 90% of Al(OH).sub.3 particles in the pulverulent release agent have a particle diameter of less than 3.5 micrometers.

20. The method according to claim 1, wherein at least 90% of AlO(OH) particles in the pulverulent release agent have a particle diameter of less than 1 micrometer.

21. The method according to claim 1, wherein at least 90% of AlO(OH) particles in the pulverulent release agent have a particle diameter of less than 0.7 micrometer.

22. The method according to claim 4, wherein at least 90% of dehydroxylated kaolin particles in the pulverulent release agent have a particle diameter of less than 5 micrometers.

23. The method according to claim 4, wherein at least 90% of dehydroxylated kaolin particles in the pulverulent release agent have a particle diameter of less than 4 micrometers.

24. The method according to claim 1, which further comprises mixing the combustible particles with the pulverulent release agent in a mixer.

25. The method according to claim 1, wherein the furnace is a rotary tube furnace or a directly heated rotary tube furnace.

26. The method according to claim 1, wherein the furnace is a shaft furnace.

27. The method according to claim 1, which further comprises setting a combustion temperature to a value between 800° C. and 1150° C.

28. The method according to claim 1, which further comprises setting a combustion temperature to a value between 850° C. and 1000° C.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

(1) FIG. 1 is a greatly diagrammatically simplified representation of a plant for producing hollow glass microspheres, having a mixer for mixing combustible particles with a pulverulent release agent composed of AlO(OH), optionally in a mixture with Al(OH).sub.3 and optionally dehydroxylated kaolin, and also having a combustion furnace, implemented as a rotary tube furnace, into which the mixture of combustible particles and release agent is introduced, so that the combustible particles are expanded to form the desired hollow microspheres;

(2) FIG. 2 is a representation in accordance with FIG. 1 which shows an alternative embodiment of the plant, in which the combustion furnace is implemented as a shaft furnace;

(3) FIG. 3 is a scanning electron micrograph of a hollow glass microsphere produced in accordance with the invention, in a broken-open state; and

(4) FIG. 4 is a scanning electron micrograph, at greater magnification than FIG. 3, of the broken-open glass wall of a hollow microsphere produced in accordance with the invention.

DETAILED DESCRIPTION OF THE INVENTION

(5) Referring now in detail to the figures of the drawings, in which structures and parts that correspond to one another are provided consistently with the same reference symbols, and first, particularly, to FIG. 1 thereof, there is seen a plant 1 for producing hollow glass microspheres M, i.e., for producing hollow glass spheres having typical diameters which are predominantly, for example, in a range of between 40 and 350 micrometers.

(6) The plant 1 includes a first silo 2 as reservoir vessel for combustible particles G, and also a second silo 3 as a reservoir vessel for pulverulent release agent T. Additionally, the plant 1 includes a mixer 5 for mixing the combustible particles G with the release agent T, and also a combustion furnace, implemented as rotary tube furnace 6, for expanding the combustion particles G to form the desired hollow microspheres M.

(7) The combustible particles G stored in the first silo 2 are approximately spherical particles whose diameters are, for example, approximately in the range between 20 micrometers and 200 micrometers. The combustible particles G are produced preferably by spray granulation. Starting materials for that process, including finely ground glass, waterglass, and an expander (e.g., soda niter, sugar, or glycerol), are used to prepare a highly mobile suspension (slip) with water, and this suspension is sprayed in a spraying tower in order to form the combustible particles G. The combustible particles G are subsequently dried. Drying is followed optionally by classifying, where the fraction having the desired diameters is selected and supplied to the silo 2.

(8) In the embodiment of the plant 1 that is shown, the mixer 5 is implemented as an Eirich intensive mixer. The mixer 5 in this case includes a substantially cup-shaped mixing vessel 10, which is mounted rotatably about its longitudinal axis 11, which is inclined relative to the vertical. A mixing tool 12, which is rotatable counter to the mixing vessel 10, is disposed eccentrically in the mixing vessel 10, in parallel to the longitudinal axis 11. The mixing vessel 10 can be charged by way of a closable lid opening 15 and can be emptied through a likewise closable and centrally disposed base opening 16. In exemplary sizing, the mixer 5 in this embodiment has a power input of 10 to 20 kilowatts per 100 kg mixture (preferably about 15 kilowatts per 100 kg mixture) and a peripheral velocity at the outermost point of the stirring tool of at least 30 meters per second. In alternative embodiments, however, the plant 1 may also include a different kind of mixer, such as a drum mixer, for example.

(9) The rotary tube furnace 6 conventionally includes an elongated, hollow-cylindrical rotary tube 20 made from steel which is resistant to high temperatures, with a combustion chamber 21 formed in the interior of the tube. The rotary tube 20 is mounted rotatably about its longitudinal axis 23, which is disposed with a slight incline relative to the horizontal. As shown, the rotary tube furnace is constructed as a directly heated rotary tube furnace. The combustion chamber 21 in this case is fired directly with a gas-operated burner 26, which is disposed at the output end of the rotary tube 20.

(10) In the operation of the plant 1, combustible particles G and release agent T are metered from the two silos 2, 3 onto a mixing chute 30 which is disposed beneath the silos 2, 3, so that at that point there is a premix composed of combustible particles G and release agent T, with a specified release agent fraction. The desired mass ratio is set by using a balance, for example. Alternatively, the setting is performed volumetrically, by using conveying screws or star wheels assigned to the silos 2, 3, for example. Via the mixing chute 30, the premix of combustible particles G and release agent T is conveyed into the mixing vessel 10 of the mixer 5.

(11) Alternatively to the exemplary representation, there may also be no mixing chute 30, in which case combustible particles G and release agent T are each metered separately into the mixer 5, so that the desired mixing ratio is generated there.

(12) The mixing procedure takes place batchwise, with one batch of the premix being subjected to a mixing procedure in each case. The premix of release agent T and combustible particles G is homogenized in the mixer 5 for a mixing time of 1 to 10 minutes. After the end of the mixing procedure, the mixture of combustible particles G and release agent T is discharged from the mixing vessel 10 through the base opening 16. The mixture is optionally stored in a buffer vessel (not shown explicitly) which is placed between the mixer 5 and the rotary tube furnace 6.

(13) From the mixing chute 30 or the optional downstream buffer vessel, the mixture of combustible particles G and release agent T is supplied continuously, by using a charging facility which is not shown explicitly herein, to the combustion chamber 21 of the rotary tube furnace 6 (indicated by an arrow 31). In the combustion chamber 21, in the operation of the plant 1, the burner 26 is used to generate a specified combustion temperature, at which the combustible particles G undergo successive expansion to form the desired hollow microspheres M within a period of around 1 to 15 minutes.

(14) The hollow microspheres M produced are discharged from the combustion chamber 21 and, after a cooling and sorting step, are supplied to a product reservoir (not shown herein). The release agent T is separated from the hollow microspheres M by sieving or pneumatic classifying. Optionally, again by sieving or pneumatic classifying, the hollow microspheres M are separated from particles which have undergo multicellular (foamlike) expansion (that is, particles having a plurality of large cavities), which may be formed during the combustion process alongside the hollow microspheres M. These multicellularly expanded particles are either discarded as rejects or supplied for an alternative use.

(15) FIG. 2 shows an alternative embodiment of the plant 1. In contrast to the first embodiment, the expansion process in this case is carried out not in a rotary tube furnace but instead in a shaft furnace 40.

(16) The shaft furnace 40 includes a combustion chamber 41 which is extended in the manner of a shaft and aligned vertically with respect to the longitudinal extent, this chamber 41 being surrounded by a double jacket 42 of steel that is insulated thermally with respect to the outside. Cooling air K is guided in a cooling gap 43 which is formed by the double jacket 42. Toward the top, the combustion chamber 41 is widened in a steplike manner.

(17) Assigned to the shaft furnace 40 is a gas-operated burner 45, which is used to generate a hot gas stream H, within the combustion chamber 41, that is directed from bottom to top. For this purpose, the hot gas generated by the burner 45 is supplied through a hot gas line 46 to the combustion chamber 41 as hot gas stream H. At approximately half the height of the combustion chamber 41, specifically in the region of the above-described cross-sectional widening, there are a number (six, for example) of additional gas-operated burners 47, which are positioned in a crownlike distribution around the periphery of the combustion chamber 41.

(18) Adjoining the combustion chamber 41 at the top, according to FIG. 2, is a region which serves as a cold trap 50 and which has a cross section widened further relative to the cross section of the upper portion of the combustion chamber 41. Alternatively, the combustion chamber 41 and also the optional cold trap 50 may be implemented with a uniform cross section over the whole of their height.

(19) The shaft furnace 40, finally, includes a charging facility, formed in this case by a combustibles line 55. The combustibles line 55 is passed through the double jacket 42 and opens into the lower portion of the combustion chamber 41. The combustibles line 55 is fed from the mixer 5 or from an optionally downstream buffer vessel (indicated by the arrow 56). The combustibles line 55 runs in particular with a descent in the charging direction, so that without active conveying (merely under the action of gravity) the combustible material slides into the combustion chamber 41. Optionally, however, the charging facility may also include a device for the active conveying of the combustible material—for example, a compressed air system or a conveying screw.

(20) In the operation of the plant 1, in the exemplary embodiment above, the homogeneous mixture of combustible particles G and release agent T is conveyed continuously by using the combustibles line 55 into the combustion chamber 41, where it is captured by the hot gas stream H and carried upward.

(21) In the lower portion of the combustion chamber 41, a temperature is generated of around 650° C., for example, at which the combustible particles G are first of all preheated. The combustion chamber 41 is additionally heated by the burners 47, and so the temperature in the upper portion of the combustion chamber 41 is increased to the combustion temperature which exceeds the softening temperature of the finely ground glass. The expansion of the combustible particles G to form the hollow microspheres M takes place in this case in brief flame contact at approximately 1400° C.

(22) The expanded hollow microspheres M are supplied, finally, to the cold trap 50, where they are quenched by supply of cooling air K. Finally, the hollow microspheres M are isolated from the hot gas stream through a solids separator, and, optionally after a sorting step, they are supplied to a product reservoir (again not shown herein). The entrained release agent T and also, optionally, any rejects (especially multicellularly expanded particles) are separated in turn from the hollow microspheres M by using a cyclone.

INVENTIVE EXAMPLE 1

(23) 91 wt % of finely ground used glass (d97≈50 μm), 7 wt % of waterglass and 2 wt % of soda niter were admixed with water to produce a highly mobile slip, which was subsequently granulated in a spraying tower. For the present example, the fine particle fraction of the sprayed granules was employed, this fraction being discharged from the spraying tower with the air stream and deposited in a downstream cyclone. The combustible particles thus obtained have a particle size distribution of d.sub.10≈30 μm, d.sub.50≈80 μm and d.sub.90≈175 μm.

(24) The dried combustible particles were mixed for five minutes in an Eirich intensive mixer with the release agent, composed in this case of AlO(OH) (particle size distribution: d.sub.10=0.2 μm; d.sub.50=0.35 μm; d.sub.90=0.6 μm; purity: 99.7%) in the following proportions: 83.3 wt % combustible particles 16.7 wt % release agent (AlO(OH))

(25) This mixture was subsequently expanded in an indirectly heated rotary tube furnace (pilot scale). In this and all the experiments described below, the combustion temperature was varied during the progress of the experiment, until hollow microspheres were produced (at the combustion temperatures stated; in the case of inventive example 1, at a combustion temperature of 960° C.).

(26) This experiment produced hollow microspheres which in part, however, had an non-round shape.

INVENTIVE EXAMPLE 2

(27) The combustible particles produced in the same way as for inventive example 1 were again mixed for five minutes in an Eirich mixer with the release agent, which in this case was formed of AlO(OH) (as in inventive example 1) and Al(OH).sub.3 (particle size distribution: d.sub.10=0.6 μm; d.sub.50=1.3 μm; d.sub.90=3.2 μm; purity: 99.5%) in the following proportions: 83.3 wt % combustible particles 16.7 wt % release agent (8.35 wt % AlO(OH) and 8.35 wt % Al(OH).sub.3)

(28) This mixture was expanded in the same way as for inventive example 1 in the indirectly heated rotary tube furnace (pilot scale) at a combustion temperature of 960° C.

(29) This experiment produced hollow microspheres which overall had a rounder shape than the hollow microspheres from inventive example 1. Moreover, the hollow sphere walls visually had a more homogeneous (“more strongly vitrified”) structure. In this experiment as well, however, particles with an unround form were visible. Moreover, alongside individual hollow microspheres, there were also agglomerates.

INVENTIVE EXAMPLE 3

(30) The combustible particles produced in the same way as for inventive example 1 were mixed in this case for 20 minutes in a drum mixer with the release agent, which in this case was formed of AlO(OH) (as in inventive example 1) and Al(OH).sub.3 (as in inventive example 2), in the following proportions: 70 wt % combustible particles 30 wt % release agent (15 wt % AlO(OH) and also 15 wt % Al(OH).sub.3)

(31) In contrast to inventive examples 1 and 2, this mixture was expanded in a directly heated industrial rotary tube furnace (production scale) at a combustion temperature of 926° C.

(32) This experiment produced hollow microspheres having good sphericity and a visually approximately homogeneous (“vitrified”) hollow sphere wall. There were no agglomerates.

INVENTIVE EXAMPLE 4

(33) The combustible particles produced in the same way as for inventive example 1 were mixed in this case in analogy to inventive example 3 for 20 minutes in the drum mixer with the release agent, which in this case was formed of AlO(OH) (as in inventive example 1) and Al(OH).sub.3 (as in inventive example 2), in the following proportions: 77 wt % combustible particles 23 wt % release agent (8 wt % AlO(OH) and also 15 wt % Al(OH).sub.3)

(34) In the same way as for inventive example 3, this mixture was expanded in the directly heated rotary tube furnace (production scale) at a combustion temperature of 882° C.

(35) This experiment likewise produced hollow microspheres having good sphericity and a visually approximately homogeneous (“vitrified”) hollow sphere wall. There were only sporadic agglomerates.

INVENTIVE EXAMPLE 5

(36) The combustible particles produced in the same way as for inventive example 1 were mixed in this case for 5 minutes in the Eirich mixer with the release agent, which in this case was formed of AlO(OH) (as in inventive example 1) and Al(OH).sub.3 (as in inventive example 2), in the following proportions: 81.1 wt % combustible particles 18.9 wt % release agent (4.7 wt % AlO(OH) and also 14.2 wt % Al(OH).sub.3)

(37) In the same way as for inventive example 1, this mixture was expanded in the indirectly heated rotary tube furnace (pilot scale) at a combustion temperature of 960-990° C.

(38) This experiment likewise produced hollow microspheres having good sphericity and a visually approximately homogeneous (“vitrified”) hollow sphere wall. In spite of the increase in the combustion temperature to 990° C., there were only a few agglomerates.

INVENTIVE EXAMPLE 6

(39) The combustible particles produced in the same way as for inventive example 1 were in this case mixed for five minutes in the Eirich mixer with the release agent, which in this case was formed of AlO(OH) (as in inventive example 1), Al(OH).sub.3 (as in inventive example 2), and calcined kaolin (particle size distribution: d.sub.10=1 μm; d.sub.50=2 μm; d.sub.90=10 μm), in the following proportions: 70 wt % combustible particles 30 wt % release agent (6 wt % AlO(OH) and also 19 wt % Al(OH).sub.3 and also 5 wt % calcined kaolin)

(40) In the same way as for inventive example 3, this mixture was expanded in the directly heated rotary tube furnace (production scale) at a combustion temperature of 828° C.

(41) This experiment likewise produced hollow microspheres of high quality.

COMPARATIVE EXAMPLE 1

(42) The combustible particles produced in the same way as for inventive example 1 were in this case mixed for 5 minutes in the Eirich mixer with the release agent, which in this case was formed of fine-particle Al(OH).sub.3 (particle size distribution: d10=0.3 μm; d.sub.50=0.4 μm; d.sub.90=0.8 μm; purity: 99.3%), in the following proportions: 88.9 wt % combustible particles 11.1 wt % release agent (Al(OH).sub.3)

(43) This mixture was expanded in an indirectly heated rotary tube furnace (pilot scale) at a combustion temperature of 846-970° C.

(44) This experiment produced almost exclusively agglomerates.

COMPARATIVE EXAMPLE 2

(45) The combustible particles produced in the same way as for inventive example 1 were mixed in this case for 5 minutes in the Eirich mixer with the release agent, which in this case was formed of Al(OH).sub.3 (as in inventive example 2), in the following proportions: 75 wt % combustible particles 25 wt % release agent (Al(OH).sub.3)

(46) In the same way as for inventive example 3, this mixture was expanded in the directly heated rotary tube furnace (production scale) at a combustion temperature of 720° C.

(47) In this experiment it was not possible to obtain any satisfactory product quality. Besides hollow microspheres, the expanded material included a high fraction of rejects (particles having undergone multicell expansion).

COMPARATIVE EXAMPLE 3

(48) The combustible particles produced in the same way as for inventive example 1 were mixed in this case for 5 minutes in the Eirich mixer with the release agent, which in this case was formed of Al(OH).sub.3 (as in inventive example 2), in the following proportions: 76 wt % combustible particles 24 wt % release agent (Al(OH).sub.3)

(49) In the same way as for inventive example 3, this mixture was expanded in the directly heated rotary tube furnace (production scale) at a combustion temperature of 800° C.

(50) In this experiment, it was not possible to maintain stable production of hollow microspheres. After initial production of high-quality hollow microspheres, there were increasingly agglomerates and reject particles (particles having undergone multicell expansion).

COMPARATIVE EXAMPLE 4

(51) The combustible particles produced in the same way as for inventive example 1 were mixed in this case for 5 minutes in the Eirich mixer with the release agent, which in this case was formed of metakaolin, in the following proportions: 75 wt % combustible particles 25 wt % release agent (metakaolin)

(52) In the same way as for inventive example 3, this mixture was expanded in the directly heated rotary tube furnace (production scale) at a combustion temperature of 862° C. to 930° C.

(53) The product resulting from this experiment was formed almost exclusively of particles having undergone multicellular expansion. No agglomerates were observed.

(54) Analysis of Hollow Microspheres from Inventive Example 5

(55) FIGS. 3 and 4 show scanning electron micrographs of broken-open hollow microspheres M, produced in the experiment described in the form of inventive example 5. From FIG. 3 it is apparent that the hollow microspheres M depicted herein, with a diameter of around 70 micrometers, are formed by a single, central and spherical cavity 60, surrounded by a thin glass wall 61 with a thickness of around 2 to 5 micrometers. From FIGS. 3 and 4 it is apparent that aluminum oxide particles 63 are fused within a radially outer layer 62 of the glass wall 61, whose radial extent is around 1 micrometer. The glass wall 61 in this case has a two-phase construction, which is also evident in the micrograph of FIG. 4, with this two-phase construction delimiting the outer layer 62 from a remaining inner region 64 of the glass wall 61.

(56) Through energy-dispersive x-ray spectroscopy (EDX) on the hollow microspheres M it was possible to demonstrate that the two-phase construction of the wall material, evident under the scanning electron microscope, is combined with a gradient in the chemical composition of the wall material, reflected in particular in the aluminum content. Whereas a chemical composition measured in the inner region 64 of the glass wall 61 was typical of a lime-soda glass, with an aluminum content of 1.16 wt %, the EDX measurement for the aluminum content of the outer layer 62 produced an estimate of around 14 wt %.

(57) The following is a summary list of reference numerals and the corresponding structure used in the above description of the invention:

LIST OF REFERENCE SYMBOLS

(58) 1 plant 2 silo 3 silo 5 mixer 6 rotary tube furnace 10 mixing vessel 11 longitudinal axis 12 mixing tool 15 lid opening 16 base opening 20 rotary tube 21 combustion chamber 23 longitudinal axis 25 cladding 26 burner 30 mixing chute 31 arrow 40 shaft furnace 41 combustion chamber 42 jacket 43 cooling gap 45 burner 46 hot gas line 47 burner 50 cold trap 55 combustibles line 56 arrow 60 cavity 61 glass wall 62 (outer) layer 63 aluminum oxide particles 64 (inner) region G combustible particles H hot gas stream K cooling air M hollow microspheres T release agent