DEVICE AND METHOD FOR TEMPERATURE-OPTIMIZED MECHANO-CHEMICAL ACTIVATION

Description

[0001] The invention relates to a process for the thermally controlled mechano-chemical activation of mineral materials, in particular clays.

[0002] Activated clays have established themselves as an additive, particularly in the cement industry. The current method is drying and calcining the clays, i.e., thermal activation. This requires energy for heating, and the high temperature can also cause further, potentially undesirable, changes in the material. Furthermore, the thermal process requires flue gas purification to capture the resulting nitrogen oxide and sulfur oxide emissions. Furthermore, the thermal process will require the use of processes to capture and, if necessary, purify the carbon dioxide produced or released.

[0003] Therefore, the so-called mechanical activation or mechano-chemical activation by intensive grinding is increasingly being discussed.

[0004] During mechanochemical activation, previously crystalline water remains in the mineral material, for example, as inner-layer water (xerogels). This differentiation from thermally activated materials is a key quality feature of mechanochemically activated materials when used as cement aggregates, as it results in improved binding properties, particularly low water requirements. This has an improved impact on, for example, the strength development and processing of the binder-containing mortar or concrete, without the need for expensive cement additives such as superplasticizers.

[0005] From the subsequently published DE 10 2023 106 210 a process for grinding and pozzolanic activation in a stirred ball mill is known.

[0006] From the subsequently published DE 10 2023 106 217, a process for grinding and pozzolanic activation in two separate stages of a stirred ball mill is known.

[0007] From the subsequently published DE 10 2023 106 221, the combination of mechanical and thermal activation in at least one agitator ball mill is known.

[0008] The subsequently published DE 10 2023 106 222 describes the color optimization during the mechanical activation of clays.

[0009] From the subsequently published DE 10 2023 123 525 a cement additive made from old concrete is known.

[0010] One advantage of mechanochemical activation is that even clays with a lower kaolin content, which are not suitable for thermal activation, can be mechanochemically activated. This broadens the available raw material base.

[0011] One of the challenges with mechanical activation is that only about 25% of the applied milling energy is actually converted into chemical energy (activation), while about 75% is converted into heat. This heat leads to heating of the product. Therefore, there is a risk that the material will be overheated and thus lose its beneficial properties. The difficulty, however, is that the energy for sufficient mechanical activation must be introduced into the material itself, so a simple reduction of the applied energy is not possible.

[0012] A temperature-controlled ball mill is known from CN 110 586 265 A.

[0013] An ultra-fine cementitious mortar is known from US 5 776 244 A.

[0014] ES 2 245 564 B1 discloses a water injection system for a mill with two controlled atomizers to spray water individually into two chambers of the mill and to regulate the mill temperature.

[0015] From US 2014 / 263 768 A1 a mechanical mill, a toner production device and a toner production method are known.

[0016] The object of the invention is to provide a process which is as gentle as possible and yet leads to a sufficiently activated product.

[0017] This object is achieved by the method having the features specified in claim 1. Advantageous further developments emerge from the subclaims, the following description, and the drawing.

[0018] A device for carrying out the method according to the invention serves for the mechanical activation of a mineral material, for example, clay. Activation is conventionally carried out thermally, whereby the mineral material is heated, for example, to 900°C to 1000°C. The objective of activation is achieved in mechanical activation through very intensive grinding, whereby significantly more energy is introduced than is required for comminution. In this range of mechanical activation, particle growth is detectable through grinding. Specifically, this means that, despite further energy absorption by the particles, a coarsening of the grain size range can be detected using conventional analytical methods. The device comprises a mill. The mill is preferably an agitated ball mill.Such devices are known, for example, from DE 10 2023 106 210, DE 10 2023 106 217, DE 10 2023 106 221, DE 10 2023 106 222, or DE 10 2023 123 525. The mill has a drive. The energy is introduced into the mill via the drive. The device has at least a first temperature sensing element. A temperature sensing element can be contact-based or contactless. The temperature sensing element can be a thermocouple, for example, or it can also be designed as an IR sensor. The device preferably has several temperature sensing elements. The first temperature sensing element is arranged in or on the mill. In the simplest case, it is arranged on the outside of the mill housing. The advantages are the simple arrangement, easy connection, avoidance of wear due to ground material, and the like.The measurement is the least accurate, averaged over the total mass of the mill and subject to a time delay. A particularly accurate method would be non-contact measurement of the temperature of the material to be ground within the mill, for example using IR sensors. The challenge here is particularly dust formation, adhesion, and wear caused by the material to be ground. The device has a control device. The device also has a material feed for feeding the material to be ground to the mill. The control device is connected to the first temperature sensing element for transmitting the measured temperature. Furthermore, the control device is connected to the drive for regulating the drive power and to the material feed for regulating the amount of material fed in.It is essential that both the energy input (control of the drive power) and the quantity of ground material fed in are regulated, since a high grinding energy input of, for example, 200 kWh / t of ground material is approximately constant for mechanical activation. Therefore, simply reducing the energy input would result in insufficient activation.

[0019] When grinding a material, three stages can be observed depending on the energy input. In the first stage, the particle size decreases (more or less linearly) with the energy input (Rittinger zone). Put simply, the more you grind, the finer the product becomes. However, there is a limit to this, a particle size that can hardly be exceeded. From this point on, a second stage follows, in which the particle size cannot be changed any further with further energy input (aggregation zone). For economic reasons, the transition from the first to the second stage is avoided during grinding, as there is no further comminution effect for the additional effort. If the energy input is increased even further, a third stage can be reached, in which a further increase in the particle size can be observed (agglomeration zone).This area is therefore much more likely to be avoided during grinding, as a better result in terms of particle size distribution can be achieved with less effort.

[0020] However, it has been shown that high energy inputs, i.e., in the third stage, lead to changes in the material itself. In clays, for example, just like thermal activation, this leads to activation, i.e., to a reactivity that enables its use as a binder (and thus as a clinker substitute). This third stage is therefore the mechanochemical activation and differs from the grinding, which is carried out in the first stage. Thus, grinding according to the state of the art is not mechanochemical activation, and not every state-of-the-art mill is suitable for mechanochemical activation.

[0021] In a further embodiment of the invention, the mill has a cooling device. The cooling device is arranged in or on the housing of the mill or is a component of the housing. In addition, the cooling device can also be arranged, for example, in the shaft in the mill. The control device is connected to the cooling device to regulate the cooling output. The cooling device is usually operated with a cooling fluid, in particular water, and is therefore capable of absorbing and transporting large amounts of heat. Due to its external arrangement, the cooling is sluggish, particularly with regard to control. On the other hand, the cooling fluid inlet temperature can be subject to fluctuations, for example due to weather conditions. If, for example, the cooling water temperature rises due to weather conditions, the efficiency of the cooling by a cooling device can decrease and thus lead to an increase in the temperature inside.

[0022] In a further embodiment of the invention, the first temperature sensing element is arranged at a position selected from the group comprising the mill housing, the mill shaft, and the mill product outlet. As already explained, an arrangement on the housing is simple. An arrangement on or in the shaft is also simple, but mechanical stress can lead to wear. Another option is therefore to measure the product temperature directly at the mill product outlet, thus outside the grinding chamber.

[0023] Of course, any combination can also be selected if several temperature sensing elements are used.

[0024] In In a further embodiment of the invention, the first temperature sensing element is arranged behind an outlet rotor in a discharge area, preferably in the front third of the discharge area. The arrangement of the temperature sensing element is optimized such that the temperature of the ground material in the mill can be measured as accurately as possible, which is difficult or impossible due to the movement directly inside the mill during grinding. Measurements on the housing or the wall have only limited accuracy and time resolution, partly due to any cooling devices present there, but at least due to their high heat capacity. This arrangement is therefore particularly well suited to taking the most timely and accurate temperature measurement of the ground material itself and thus accurately reflecting the reality inside the mill.

[0025] In In a further embodiment of the invention, the first temperature sensing element is designed for contactless temperature detection of the temperature of the material to be ground in the mill. This most complex and challenging method, however, has the advantage that the temperature of the material to be ground is detected directly. This eliminates any time delay caused by the thermal inertia of the overall system. Furthermore, an upper temperature limit TG can be set based on material knowledge and does not need to be adapted to the thermal behavior of the entire device. Contactless temperature detection is preferably carried out using infrared measurement.

[0026] In a further embodiment of the invention, the mill has an internal volume of at least 1 m 3<.

[0027] In a further embodiment of the invention, the mill has an energy density of at least 200 kW / m 3<.

[0028] In a further embodiment of the invention, the mill has a length of at least 2 m, preferably at least 2.5 m.

[0029] In a further embodiment of the invention, the mill has a cross-sectional area perpendicular to the longitudinal axis of at least 0.71 m 2< , preferably of at least 0.75 m 2< .

[0030] In a further embodiment of the invention, the mill has a length to diameter ratio of at least 3, preferably of at least 3.5.

[0031] The invention relates to a method for mechanically activating a mineral material using a mill. Such methods are known, for example, from DE 10 2023 106 210, DE 10 2023 106 217, DE 10 2023 106 221, DE 10 2023 106 222, or DE 10 2023 123 525. The method comprises the following steps: a) Specifying an upper temperature limit TG , b) Continuously recording the temperature T of the mill and / or the material to be ground, c) Comparing the recorded temperature T with the upper temperature limit TG , d) Adjusting the drive power of the mill and the supplied amount of material to be ground depending on the comparison in step c).

[0032] In addition to the conventional process, temperature monitoring is used to prevent the product from overheating and losing the valuable properties of mechanical activation, making it similar to a thermally activated product.

[0033] It is crucial that in step d) the grinding energy and the amount of material to be ground are adjusted so that the high energy input required for mechanical activation is maintained. Likewise, at a lower temperature, for example, the throughput can also be increased by increasing both the energy input and the material input.

[0034] The measurement in step b) can be carried out in the simplest form on the outside of the mill housing. This facilitates integration and avoids wear. However, this measurement method is the least accurate due to the inertia of the overall system. Furthermore, the temperature measured here is lower than the temperature of the material being ground. The best method is to measure the material being ground inside the mill, for example, using a non-contact IR sensor. The challenge here is the integration into the grinding chamber with its strong mechanical stresses and the dust development inside the grinding chamber. The measurement can also be taken, for example, on the product exiting the mill.

[0035] The comparison in step c) can be done digitally. Exceeding the limit leads to a reduction in the drive power and the supplied quantity of ground material in step d), and falling below the limit leads to an increase in the drive power and the supplied quantity of ground material in step d). Preferably, however, an adjustment can also be made depending on the distance between the temperature recorded in step b) and the upper temperature limit TG. For example, the closer the recorded temperature T approaches the upper temperature limit TG, the more the drive power and the supplied quantity of ground material can be reduced in step d). On the other hand, the further the recorded temperature T moves away from the upper temperature limit TG, the more the drive power and the supplied quantity of ground material are increased in step d).

[0036] During the adjustment in step d), the energy input per quantity of milled material can preferably be kept constant, for example, at 500 kWh / t. This ensures consistent activation quality.

[0037] However, there is not necessarily a direct relationship between drive power and the amount of ground material supplied, as there are also other adjustment options, such as additional cooling.

[0038] Particularly preferably, the upper temperature limit TG is set between 250 °C and 300 °C.

[0039] In a further embodiment of the invention, a temperature operating range is additionally specified. The temperature range is preferably below the upper temperature limit TG or can have this. The temperature operating range has an upper range limit T BO and a lower range limit T BU. The upper temperature limit T BO can be the same as the upper temperature limit TG. If it is determined that the temperature T falls below the lower range limit T BU, the drive power and the supplied quantity of ground material are increased. If it is determined that the temperature T exceeds the upper range limit T BO, the drive power and the supplied quantity of ground material are reduced. The use of such a temperature range facilitates control.

[0040] In a further embodiment of the invention, the temperature of the material being ground exiting the mill is measured. Measuring it at the exit is easier than measuring it directly in the mill. One disadvantage is that a time lag occurs due to the transport through the mill, meaning that the measurement is only performed after the grinding process has been completed.

[0041] In a further embodiment of the invention, the gas flow through the mill is adjusted depending on the comparison in step c). The gas flow through the mill can dissipate some of the heat and thus achieve cooling. However, due to the low heat capacity of the gas flow, this is limited.

[0042] In a further embodiment of the invention, the cooling capacity of the mill is adjusted depending on the comparison in step c). Cooling preferably takes place in the mill housing. Optionally, cooling can also be provided in the shaft.

[0043] In a further embodiment of the invention, when the upper temperature limit TG is exceeded, direct cooling is carried out by water injection in order to achieve fast and efficient cooling.

[0044] In a further embodiment of the invention, the reactivity of the material leaving the mill is measured. This reactivity measurement can be performed inline, but due to the complexity of the process, analysis is preferably performed after sampling, particularly examining the setting behavior. Especially when temperature measurement is only performed on the mill housing, this can be a significant additional indicator of exceeding the upper temperature limit TG.

[0045] In a further embodiment of the invention, the adjustment in step d) is also carried out depending on the detected reactivity. Exceeding the upper temperature limit TG is indicated by a decrease in reactivity or an increased water requirement.

[0046] In a further embodiment of the invention, the mill is operated with a residence time of the material to be ground in the mill of at least 5 minutes, preferably at least 10 minutes, particularly preferably at least 20 minutes.

[0047] The method according to the invention is explained in more detail below using the device based on an embodiment shown in the drawing. Fig. 1Device with control device

[0048] In Fig. 1An exemplary device is shown. The core of the mechanical activation is a mill 10, for example and preferably a stirred ball mill. The mill is driven by a drive 20. The material to be ground is supplied via a material feed 50, and gas can be supplied via a gas feed 60. The ground product is analyzed using a reactivity measuring device 70. The reactivity measuring device 70 is, for example, a calorimeter. Furthermore, the mill 10 has a cooling jacket 80.

[0049] Furthermore, the device has a control device 40, which is connected in particular to the temperature sensing element 30. The other components are controlled according to the temperature T detected there and a comparison with an upper temperature limit TG. If the temperature T rises close to or above TG, the coolant flow through the cooling jacket 80 and / or the gas flow through the gas feed 60 can be increased, for example. It is important, however, that the power of the drive 20 and the supplied quantity of ground material through the material feed 50 can also be reduced. If the temperature T drops, the device can be started up again and the power of the drive 20 and the supplied quantity of ground material through the material feed 50 can be increased again. Reference symbol

[0050] 10Mill 20Drive 30Temperature sensing element 40Control device 50Material feed 60Gas feed 70Reactivity measuring device 80Cooling jacket

Claims

1. A method for mechanically activating a mineral material by means of a mill (10), wherein the method comprises the following steps: a) specifying an upper temperature limit TG, b) continuously detecting the temperature T of the mill (10) and / or the milling material, c) comparing the detected temperature T with the upper temperature limit TG, d) adjusting the drive power of the mill (10) and the supplied quantity of milling material on the basis of the comparison in step c).

2. The method according to claim 1, characterized in that an operating temperature range is additionally specified, wherein the operating temperature range has an upper range limit TBO and a lower range limit TBU, wherein, when it is determined that the temperature T has fallen below the lower range limit TBU, the drive power and the supplied quantity of milling material are increased, wherein, when it is determined that the temperature T has exceeded the upper range limit TBO, the drive power and the supplied quantity of milling material are decreased.

3. The method according to any of claims 1 to 2, characterized in that the temperature of the milling material emerging from the mill (10) is detected.

4. The method according to any of claims 1 to 3, characterized in that the gas stream guided through the mill (10) is adjusted on the basis of the comparison in step c).

5. The method according to any of claims 1 to 4, characterized in that the cooling power of the mill (10) is adjusted on the basis of the comparison in step c).

6. The method according to any of claims 1 to 5, characterized in that the reactivity of the milling material emerging from the mill (10) is detected.

7. The method according to claim 6, characterized in that the adjustment in step d) additionally also takes place on the basis of the detected reactivity.