A multi-step method for manufacturing multiphase materials

Abstract

The multi-step method of making MPM includes at least a first step and a second step. The first step can be carried out at a relatively low temperature and / or a relatively low pressure. The second step can be carried out at a relatively high temperature and / or a relatively high pressure. The first step can be carried out in one or more reaction vessels and the second step can be carried out in one or more different reaction vessels.

Description

[Technical Field]

[0001] Cross-references to related applications This application claims priority to U.S. Application 63 / 214,958, filed on 25 June 2021, the contents of which are incorporated herein by reference.

[0002] field This disclosure provides a multi-step method for manufacturing multiphase materials (MPMs). [Background technology]

[0003] background A single-step method for producing MPM using an autoclave is known. [Overview of the Initiative]

[0004] overview This disclosure provides a multi-step method for producing MPM. Optionally, the method can be carried out with relatively low capital expenditures and / or relatively low operating expenses. In some embodiments, such advantages can be achieved by using relatively inexpensive equipment. As an example, in certain embodiments, the method is carried out without using an autoclave. For example, the first step can be carried out in a non-pressurized reaction vessel, which can reduce costs compared to a process using an autoclave. Furthermore, the second step can be carried out in a relatively inexpensive pressurized reaction vessel (e.g., a pipe reactor). Moreover, alternative pressurized reaction vessels, such as a pipe reactor, can allow for higher temperatures and resulting pressures compared to an autoclave.

[0005] Generally, this method comprises at least two steps. In some embodiments, the first step is carried out at a relatively low temperature (e.g., a maximum of 100°C) and / or a relatively low pressure (e.g., a maximum of 2 atmospheres). The second step includes a higher temperature and / or pressure. In some embodiments, the second step is carried out at a temperature of at least 180°C and a pressure of at least 5 atmospheres. In certain embodiments, the first step is carried out in one or more reaction vessels, and the second step is carried out in one or more different reaction vessels. The first step can be carried out with or without stirring. In some embodiments, this method may comprise more than two steps. As an example, this method may include heating to an intermediate temperature (a temperature between the lowest and highest temperatures used in the MPM formation method). In some embodiments, the method may include heating to an intermediate temperature that is at least 20°C (e.g., at least 25°C, at least 30°C, at least 35°C, at least 40°C) and up to 400°C (e.g., up to 350°C, up to 300°C, up to 290°C, up to 280°C, up to 270°C, up to 250°C, up to 240°C). This temperature can be maintained for a desired period (e.g., at least 10 minutes, at least 30 minutes, at least 1 hour, at least 10 hours) and / or up to 2 days (e.g., up to 1 day, up to 20 hours), after which it is heated to a higher temperature (e.g., the temperature to be used in the second step). Generally, there is a transition between the conditions of the first step and the conditions of the second step. As an example, in some embodiments, there is a transition between a temperature of at least 20°C and a temperature of up to 400°C. As another example, in certain embodiments, there is a transition between a pressure of up to 2 atmospheres and a pressure of at least 5 atmospheres. As a further example, in some embodiments, there is a transition between both 1) a temperature of at least 20°C and a maximum pressure of 2 atmospheres; and 2) a temperature of at least 400°C and a pressure of at least 5 atmospheres. In some embodiments, the transition is a smooth transition between one or more (e.g., all) conditions of the first step and one or more (e.g., all) conditions of the second step. For example, temperature may be a smooth transition, and / or pressure may be a smooth transition.In some embodiments, the transition of conditions is monotonic, e.g., a monotonic increase in temperature and / or a monotonic increase in pressure. In certain embodiments, the transition of conditions is stepwise, e.g., a stepwise increase in temperature and / or a stepwise increase in pressure. Other types of transitions are also possible.

[0006] Without being constrained by theory, the conditions of the first step are likely such that calcium oxide (CaO) is more soluble under these conditions, which may allow for good mass transfer of calcium ions, enabling the initial reaction between calcium and potassium feldspar to produce an intermediate product. Also without being constrained by theory, one or more steps after the first step are likely to enable a more efficient mineral conversion of the intermediate product to MPM. The multi-step reactions disclosed herein may allow for a cost-effective and efficient balance between competing factors, such as the rate of calcium ion mass transfer and MPM formation.

[0007] In one embodiment, the present disclosure provides a method for producing an MPM, comprising a) reacting starting materials at a temperature up to 100°C to form an intermediate product; and b) reacting the intermediate product at a temperature of at least 180°C, wherein the method produces an MPM.

[0008] In one embodiment, the present disclosure provides a method for producing an MPM, comprising a) reacting starting materials at a pressure of up to 2 atmospheres to form an intermediate product; and b) reacting the intermediate product at a pressure of at least 5 atmospheres, wherein the method produces an MPM.

[0009] In one embodiment, the present disclosure provides a method for producing an MPM, comprising: a) reacting starting materials to form an intermediate product; and b) reacting the intermediate product without stirring, wherein the method produces an MPM.

[0010] In one embodiment, the present disclosure provides a method for producing an MPM, comprising a) reacting starting materials in a first reaction vessel to form an intermediate product; and b) reacting the intermediate product in a second reaction vessel, wherein the second reaction vessel is different from the first reaction vessel, and the method produces an MPM.

[0011] In one embodiment, the present disclosure provides a method for producing an MPM, comprising: a) reacting starting materials at a temperature up to 100°C to form an intermediate product; and b) heating the intermediate product by a process comprising heating to a temperature of at least 180°C, wherein the method produces an MPM.

[0012] In some embodiments, a) can be carried out at temperatures up to 100°C (e.g., at temperatures up to 90°C, 80°C, 70°C, and 60°C) and / or at least 20°C.

[0013] In certain embodiments, b) can be carried out at a temperature of at least 180°C (e.g., at least 200°C, at least 210°C, at least 220°C, at least 230°C, at least 240°C) and / or at a temperature up to 400°C.

[0014] In some embodiments, a) can be carried out at a pressure of up to 2 atmospheres (e.g., up to 1.5 atmospheres, up to 1 atmosphere) and / or at a pressure of at least 0.9 atmospheres.

[0015] In certain embodiments, b) can be carried out at a pressure of at least 5 atmospheres (e.g., at least 10 atmospheres, at least 25 atmospheres, at least 50 atmospheres) and / or at a pressure of up to 300 atmospheres.

[0016] In some embodiments, the method may further include heating to a temperature of at least 180°C between a) and b).

[0017] In some embodiments, the method may further include heating to an intermediate temperature between a) and b). Optionally, in such embodiments, a) may include heating to a first temperature, b) may include heating to a second temperature, and the intermediate temperature is between the first temperature and the second temperature.

[0018] In certain embodiments, the method may further include increasing the pressure from a pressure of up to 2 atmospheres to a pressure of at least 5 atmospheres between a) and b).

[0019] In some embodiments, the method may further include increasing the pressure to an intermediate pressure between a) and b). Optionally, in such embodiments, a) may include using a first pressure, b) may include using a second pressure, and the intermediate pressure is between the first pressure and the second pressure.

[0020] In certain embodiments, a) can be carried out in a first reaction vessel and b) can be carried out in a second reaction vessel different from the first reaction vessel.

[0021] In some embodiments, a) can be carried out in a first plurality of reaction vessels and b) can be carried out in a second plurality of reaction vessels different from the first plurality of reaction vessels.

[0022] In certain embodiments, a) may include stirring the starting materials.

[0023] In some embodiments, a) does not include stirring the starting materials.

[0024] In certain embodiments, b) may include stirring the reaction product.

[0025] In some embodiments, b) does not include stirring the reaction product.

[0026] In certain embodiments, a) can be carried out using a reaction vessel selected from the group including a sealed tank, an open tank, a containment vessel, an open evaporation pond, a tubular vessel, a rotating disk, a solid-liquid contractor, and a liquid cyclone.

[0027] In some embodiments, b) can be carried out using a reaction vessel selected from the group including autoclaves, pipe reactors, three-phase gas-liquid-solid contractors, and rotating drums.

[0028] In certain embodiments, a) can be carried out for at least 15 minutes (e.g., at least 30 minutes) and / or for up to 2 weeks (e.g., up to 1 week).

[0029] In certain embodiments, b) may be carried out for at least one minute (e.g., at least five minutes) and / or for up to one week (e.g., up to 24 hours).

[0030] In certain embodiments, a) may include: a1) reacting starting materials at a first temperature up to 50°C to form a first material; and a2) after a1), reacting the first material at a second temperature higher than the first temperature to form an intermediate product. The first temperature may be at least 20°C, and the second temperature may be up to 100°C. a1) can be carried out at a temperature up to 50°C. a2) can be carried out at a temperature of at least 75°C.

[0031] In some embodiments, the method may further include drying the product of b) after b). Drying may be carried out at a temperature between at least 25°C and / or up to 400°C. Drying may occur at a pressure of at least 1 atmosphere and / or up to 100 atmospheres.

[0032] In certain embodiments, the starting material may include potassium skeleton silicate ore. The starting material may include, for example, at least one member selected from the group including potassium feldspar, calcilite, nepheline, phlogopite, muscovite, biotite, trachyte, rhyolite, mica, hyperpotassium syenite, garnet, nepheline syenite, resonite, phenite, aplite, and pegmatite. In some embodiments, the starting material may include potassium feldspar. In certain embodiments, the starting material may include at least one material selected from the group including at least one oxide, hydroxide, and carbonate of alkaline earth metals and alkali metals. In some embodiments, the starting material may include at least two materials selected from the group including at least one oxide, hydroxide, and carbonate of alkaline earth metals and alkali metals. In certain embodiments, the starting material may include at least one oxide, hydroxide, and carbonate of alkaline earth metals and alkali metals. In some embodiments, the metal may include at least one member selected from the group including lithium (Li), sodium (Na), potassium (K), beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (K). In certain embodiments, the starting material may include at least one member selected from the group including CaO, Ca(OH)2, and CaCO3.

[0033] In some embodiments, the starting materials are supplied in a single batch.

[0034] In certain embodiments, the starting materials are provided in steps.

[0035] In some embodiments, at least one of the following applies: the starting material may contain potassium skeleton silicate ore and CaO in a Ca:Si molar ratio between 0.05 and 4; the starting material may contain potassium skeleton silicate ore and Ca(OH)2 in a Ca:Si molar ratio between 0.05 and 4; and the starting material may contain potassium skeleton silicate ore and CaCO3 in a Ca:Si molar ratio between 0.05 and 4.

[0036] In certain embodiments, the starting material may include water.

[0037] In some embodiments, the starting material may include at least one member selected from the group including KCl, macronutrient sources, micronutrient sources, and sources of beneficial elements. The at least one member may include, for example, a member selected from the group including N, P, K, Ca, Mg, S, B, Cl, Cu, Fe, Mn, Mo, Ni, Zn, Na, Se, Si, Co, and V.

[0038] In certain embodiments, the method may further include, prior to b), adding to the intermediate product at least one member selected from the group comprising KCl, macronutrient sources, micronutrient sources and sources of beneficial elements. The at least one member may include a member selected from the group comprising N, P, K, Ca, Mg, S, B, Cl, Cu, Fe, Mn, Mo, Ni, Zn, Na, Se, Si, Co and V.

[0039] In some embodiments, the MPM may comprise at least two phases (e.g., at least three phases, at least four phases) selected from the group including a potassium feldspar phase, a tobermorite phase, a hydrogrossular phase, a dicalcium silicate hydrate phase, and an amorphous phase.

[0040] In certain embodiments, the MPM may include a potassium feldspar phase, a tobermorite phase, a hydrogrossular phase, a dicalcium silicate hydrate phase, and an amorphous phase.

[0041] In some embodiments, the MPM may contain at least 1 wt% of a potassium feldspar phase and / or up to 74.5 wt% of a potassium feldspar phase.

[0042] In certain embodiments, the MPM may comprise at least 0.1% by weight of tobermorite phase and / or up to 55% by weight of tobermorite phase.

[0043] In some embodiments, the MPM may comprise at least 0.1% by weight of a hydrogrossular phase and / or up to 15% by weight of a hydrogrossular phase.

[0044] In certain embodiments, the MPM may include a dicalcium silicate hydrate phase. In such embodiments, the MPM may include up to 20% by weight of the dicalcium silicate hydrate phase.

[0045] In some embodiments, the MPM may include an amorphous phase. In such embodiments, the MPM may contain up to 55% by weight of the amorphous phase.

[0046] In certain embodiments, the MPM may contain at least 0.1% by weight of KCl and / or up to 99% by weight of KCl.

[0047] In some embodiments, the MPM may include a minor component phase. In such embodiments, the MPM may further include at least 0.1% by weight of the minor component phase and / or up to 20% by weight of the minor component phase.

[0048] In certain embodiments, the MPM has a salinity index between 5% and 119%.

[0049] In some embodiments, the MPM may have a potassium feldspar phase in the range of 1% to 74.5% by weight, a tobermorite phase in the range of 0.1% to 55% by weight, a hydrogrossular phase in the range of 0.1% to 15% by weight, a discalcium silicate hydrate phase in the range of 0% to 20% by weight, an amorphous phase in the range of 0% to 55% by weight, a potassium rock salt phase in the range of 0.1% to 99% by weight, and a minor component phase in the range of 0.1% to 99% by weight.

[0050] In certain embodiments, the MPM may contain up to 20% by weight of tobermorite phase and / or the MPM may contain up to 10% by weight of discalcium silicate hydrate phase.

[0051] In some embodiments, the MPM has a cation exchange ratio of at least 10 mmol / kg.

[0052] In certain embodiments, the MPM has a cation exchange ratio of up to 2,000 mmol / kg.

[0053] In some embodiments, the proportion of K+ in the MPM may be between 5% and 55%.

[0054] In certain embodiments, the composition can be used as a fertilizer, for soil remediation, for soil decontamination, for increasing crop yield, for improving soil health, and / or for improving soil fertility. [Brief explanation of the drawing]

[0055] Exemplary embodiments of the present disclosure are provided below with reference to the drawings. [Figure 1] Figure 1 shows one embodiment of a two-stage process. [Figure 2] Figure 2 shows one embodiment of a process that includes more than two steps. [Figure 3] Figure 3 shows the experimental results when the residence time for the second step is varied (Example 1). [Figure 4] Figure 4 shows the experimental results when the temperature for the second step is varied (Example 2). [Figure 5] Figure 5 shows the experimental results when the liquid-to-solid (L:S) ratio for the entire process and the temperature for the second step are varied (Example 3). [Figure 6] Figure 6 shows the experimental results when the temperature used in the first step was changed (Example 4). [Figure 7]Figure 7 shows the experimental results when the residence time used in the first step is varied (Example 6). [Modes for carrying out the invention]

[0056] Description of exemplary embodiments Figure 1 schematically shows one embodiment of a two-step process 100 for producing MPM. In the first step 102, the starting materials are mixed in a first reaction vessel and reacted for a first period under first set of conditions to form an intermediate product. In the second step 104, the intermediate product is placed in a second reaction vessel and heated under conditions to form MPM.

[0057] Generally, the starting material comprises one or more potassium skeleton silicate particles and one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, which are then brought into contact with water. The starting material can be added via a continuous process or a batch process. Contacting the mixture with water can be done by any suitable method, such as by adding water to the mixture, or by adding the mixture to water, or by sequentially or simultaneously adding water and the mixture to a suitable reaction vessel (see discussion below). Generally, any suitable amount of water can be used. In some embodiments, excess water relative to the potassium skeleton silicate starting material is used.

[0058] In some embodiments, the potassium-skeletal silicate may be potassium feldspar, calcilite, nepheline, trachyte, rhyolite, hyperpotassium syenite, garnet, nepheline syenite, phonite, phenite, aplite, or pegmatite. Combinations of such potassium-skeletal silicates can be used.

[0059] In some embodiments, one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, include calcium oxide, calcium hydroxide, or mixtures thereof. In some embodiments, one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, include calcium hydroxide. In some embodiments, one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, include calcium oxide. In certain embodiments, one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, include lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium, and / or cesium hydroxide. In some embodiments, one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, include magnesium oxide, calcium oxide, beryllium oxide, strontium oxide, radium oxide, magnesium hydroxide, calcium hydroxide, beryllium hydroxide, strontium hydroxide, and / or radium hydroxide.

[0060] In some embodiments, the mixture comprises a calcium-containing compound and a silicon-containing compound. In various embodiments of the present disclosure, the ratio of the calcium-containing material (i.e., CaO, Ca(OH)2, CaCO3, (Ca,Mg)CO3, and combinations thereof) to the silicon-containing material (i.e., potassium-skeletal silicates) can be used to adjust the mineralogy, extractability, buffering capacity, and other properties of the composition (e.g., MPM:KCl composition). In some embodiments, the Ca:Si ratio is at least 0.05 and / or up to 4.

[0061] As noted above, the starting material may be in the form of coarser and / or finer particles. The particles can be formed by any suitable process, such as co-grinding or commuting, using methods known in the art, such as crushing and milling of dry or slurryed material using, for example, a jaw crusher, gyrately crusher, cone crusher, ball mill, pulverizing mill, rod mill, etc. The resulting mixture can be sized as desired through sieves, screens, etc., as known in the art. In some embodiments, the particles have an average particle size of 1 nanometer to 2 millimeters.

[0062] Generally, the first step 102 is carried out at temperatures up to 100°C (e.g., up to 90°C, up to 80°C, up to 70°C, up to 60°C, up to 50°C) and / or at least 20°C (e.g., at least 25°C, at least 30°C, at least 35°C, at least 40°C), including a range between those temperatures.

[0063] Generally, the first step 102 is performed at pressures up to 2 atmospheres (e.g., up to 1.8 atmospheres, up to 1.5 atmospheres) and / or at least 0.9 atmospheres (e.g., at least 1 atmosphere, at least 1.1 atmospheres), including a range between those.

[0064] In some embodiments, the first step 102 is carried out for at least 1 minute (e.g., at least 15 minutes, at least 30 minutes, at least 1 hour, at least 10 hours, at least 1 day, at least 2 days) and / or up to 2 weeks (e.g., up to 1 week, up to 6 days, up to 5 days, up to 3 days), including a range between those periods. However, in certain embodiments, the duration used for the first step may vary. For example, when using an evaporation pond (e.g., in a relatively hot and dry environment such as a desert), the first step may be carried out for longer than 2 weeks (e.g., at least 1 month).

[0065] Generally, the first step 102 can be carried out with or without stirring. In embodiments that include stirring, any suitable stirring mechanism may be used. Exemplary examples of stirring mechanisms include impellers, mixers, stirrers, and baffles.

[0066] In some embodiments, the first step 102 is carried out in a single reaction vessel. In certain embodiments, the first step 102 is carried out in multiple reaction vessels. Examples of reaction vessels that can be used in the first step 102 include sealed tanks, open tanks, containment vessels, open evaporation ponds, tubular vessels such as pipes and rotating drums, solid-liquid contractors such as rotating disks and solid-liquid fluidized beds, and liquid cyclones.

[0067] In certain embodiments, the first step 102 may include two or more substeps. The substeps may include reacting the starting materials at a first temperature to form a first material, and then heating the first material to react it to form an intermediate product. The first temperature may be, for example, up to 50°C (e.g., between 20°C and 50°C), and the second temperature may be, for example, up to 100°C (e.g., between 50°C and 100°C).

[0068] Generally, the second step 104 includes heating to convert the intermediate material into MPM. In some embodiments, the second step 104 includes using temperatures of at least 180°C (e.g., at least 190°C, at least 200°C, at least 210°C, at least 220°C, at least 230°C, at least 240°C) and / or up to 400°C (e.g., up to 350°C, up to 300°C, up to 290°C, up to 280°C, up to 270°C, up to 250°C, up to 240°C), including a range between those temperatures.

[0069] Generally, the second step 104 is carried out at pressures of at least 5 atmospheres (e.g., at least 10 atmospheres, at least 25 atmospheres, at least 50 atmospheres) and / or up to 300 atmospheres (e.g., up to 200 atmospheres, up to 100 atmospheres, up to 75 atmospheres), including a range between those.

[0070] Typically, the second step 104 is carried out for at least 1 minute (e.g., at least 5 minutes, at least 15 minutes, at least 30 minutes, at least 1 hour, at least 10 hours, at least 1 day, at least 2 days) and / or up to 2 weeks (e.g., up to 1 week, up to 6 days, up to 5 days, up to 3 days), including a range between those steps.

[0071] The second step 104 may be carried out with or without stirring.

[0072] In some embodiments, the second step 104 is carried out in a single reaction vessel, which may differ from one or more reaction vessels used in the first step 102. In certain embodiments, the second step 104 is carried out in multiple reaction vessels. One or more reaction vessels used in the second step 104 may differ from one or more reaction vessels used in the first step 102. Any reaction vessel suitable for the conditions being used can be used in the second step 104. Examples of reaction vessels that can be used in the second step 104 include autoclaves, pipe reactors, screw reactors, and three-phase gas-liquid-solid contractors such as fluidized beds and rotating drums.

[0073] Figure 2 shows a method 200 comprising a first step 202 (e.g., similar to the one described above with respect to step 102) and a second step 204 (e.g., similar to the one described above with respect to step 204). However, method 200 further includes an additional step 203 that occurs between steps 202 and 204. Step 203 typically includes heating to achieve a temperature between the temperature used in step 202 and the temperature used in step 204, and maintaining this intermediate temperature for a period of time. In some embodiments, step 203 includes maintaining a temperature between at least 20°C (e.g., at least 25°C, at least 30°C, at least 35°C, at least 40°C) and up to 400°C (e.g., up to 350°C, up to 300°C, up to 290°C, up to 280°C, up to 270°C, up to 250°C, up to 240°C). This temperature can be maintained for a desired period (e.g., at least 10 minutes, at least 30 minutes, at least 1 hour, at least 10 hours) and / or up to 2 days (e.g., up to 1 day, up to 20 hours). In some embodiments, step 203 is carried out using the same or similar pressure conditions as those used in step 204. In certain embodiments, step 203 is carried out using a pressure that is intermediate between the pressure used for step 202 and the pressure used for step 204. Generally, step 203 can be carried out with or without stirring. Step 203 is typically carried out using the same(possible) reaction vessel as that used in step 204, but it is optional to use one or more different reaction vessels for step 203 compared to step 204.

[0074] Figure 2 shows a single intermediate step 203 between the first step 202 and the second step 204, but there may be transitions between the conditions of the first step 202 and the conditions of the second step 204. That is, it is possible to have more than one intermediate step between the first step 202 and the second step 204 (e.g., more than two intermediate steps, more than five intermediate steps, more than ten intermediate steps, more than 100 intermediate steps). As an example, in some embodiments there is a transition (including more than one intermediate temperature) between a temperature of at least 20°C (e.g., at least 25°C, at least 30°C, at least 35°C, at least 40°C) and up to 400°C (e.g., up to 350°C, up to 300°C, up to 290°C, up to 280°C, up to 270°C, up to 250°C, up to 240°C). As another example, in certain embodiments there is a transition (including more than one intermediate pressure) between a pressure of up to 2 atmospheres and a pressure of at least 5 atmospheres. As further examples, in some embodiments, there are transitions between both 1) a temperature of at least 20°C and a maximum pressure of 2 atmospheres; and 2) a temperature of at least 400°C and a maximum pressure of 300 atmospheres. In such embodiments, there is one or more intermediate temperatures between the first and second processes, and one or more intermediate pressures between the first and second processes. In some embodiments, the transition between the first and second processes is a smooth transition between one or more conditions (e.g., all) of the first process and one or more conditions (e.g., all) of the second process. For example, temperature can be a smooth transition, and / or pressure can be a smooth transition. In some embodiments, the transition of conditions is monotonic, e.g., a monotonic increase in temperature and / or a monotonic increase in pressure. In certain embodiments, the transition of conditions is a stepwise transition, e.g., a stepwise increase in temperature and / or a stepwise increase in pressure. Other types of transitions are also possible. Generally, the lowest temperature in the intermediate process between process 202 and 204 is higher than the temperature used in the first process 202, and the highest temperature in the intermediate process is lower than the temperature used in the second process 204.Generally, the minimum pressure in the intermediate process between process 202 and 204 is higher than the pressure used in the first process 202, and the maximum pressure in the intermediate process is lower than the pressure used in the second process 204.

[0075] Generally, after the formation of the MPM according to the above-described steps, a drying step is carried out. In some embodiments, the drying step can be carried out at ambient temperature (e.g., by evaporating the supernatant water). In certain embodiments, the drying step is carried out at a minimum of 25°C (e.g., at least 50°C, at least 75°C) and / or up to 400°C (e.g., up to 300°C, up to 200°C, up to 150°C), including a range between those. In some embodiments, drying is carried out at a pressure of up to 100 atmospheres (e.g., up to 50 atmospheres, up to 25 atmospheres, up to 10 atmospheres) and / or at least 1 atmosphere (e.g., at least 2 atmospheres), including a range between those. In some embodiments, drying is carried out under an inert atmosphere or a reactive atmosphere. An inert atmosphere may include, for example, a noble gas (e.g., Ar) or N2. Examples of reactive atmospheres include air, oxygen, carbon dioxide, carbon monoxide, or ammonia. Mixtures of various gases can be used. Generally, the drying step can occur with or without stirring. In certain embodiments, the drying process is carried out for a period of time ranging from 1 minute to 2 days (for example, from 1 hour to 1 day).

[0076] Generally, the MPM comprises at least two phases (e.g., at least three phases, at least four phases) selected from the potassium feldspar phase, tobermorite phase, hydrogrossular phase, dicalcium silicate hydrate phase, and amorphous phase. In some embodiments, the MPM comprises the potassium feldspar phase, tobermorite phase, hydrogrossular phase, dicalcium silicate hydrate phase, and amorphous phase. In certain embodiments, the MPM comprises at least 1% by weight of the potassium feldspar phase and / or up to 74.5% by weight of the potassium feldspar phase. In some embodiments, the MPM includes at least 0.1 wt% of tobermorite phase and / or up to 55 wt% of tobermorite phase (e.g., between 0 wt% and 50 wt%, between 0 wt% and 45 wt%, between 0 wt% and 40 wt%, between 0 wt% and 35 wt%, between 0 wt% and 30 wt%, between 0 wt% and 25 wt%, between 0 wt% and 20 wt%). In some embodiments, the MPM includes at least 0.1 wt% of hydrogrossular phase and / or up to 15 wt% of hydrogrossular phase (e.g., from 0.1 wt% to 12 wt%). In certain embodiments, the MPM includes up to 20 wt% (e.g., up to 10 wt%, up to 15 wt%, up to 12 wt%) of discalcium silicate hydrate phase. In some embodiments, the MPM includes up to 55 wt% (e.g., up to 45 wt%) of amorphous phase. In certain embodiments, the MPM further includes a minor component phase (e.g., in amounts of at least 0.1% by weight and / or up to 20% by weight). In some embodiments, the MPM includes a potassium feldspar phase in the range of 1% to 74.5% by weight, a tobermorite phase in the range of 0.1% to 55% by weight, a hydrogrossular phase in the range of 0.1% to 15% by weight, a dicalcium silicate hydrate phase in the range of 0% to 20% by weight, an amorphous phase in the range of 0% to 55% by weight, a potassium rock salt phase in the range of 0.1% to 99% by weight, and a minor component phase in the range of 0.1% to 20% by weight. In some embodiments, the MPM includes up to 20% by weight of the tobermorite phase and / or up to 10% by weight of the dicalcium silicate hydrate phase.

[0077] In some embodiments, the MPM is in the form of particles. Such particles may have an average particle size of, for example, 1 nanometer to 2 millimeters.

[0078] In general, MPM can be used as desired. In some embodiments, MPM is used as a fertilizer (e.g., to provide one or more nutrients to the soil), for soil remediation (e.g., to immobilize one or more heavy metals from the soil), for soil decontamination (e.g., to remove one or more contaminants from the soil), to increase crop yield, to improve soil health, and / or to improve soil fertility. [Examples]

[0079] The experiment was conducted to evaluate the effects of residence time in both the first and second steps, the effect of temperature on both the first and second steps, and the liquid-to-solid (L:S) ratio when manufacturing MPM.

[0080] The ultrapotassium syenite used in the examples was obtained from Triunfo batholith in Pernambuco, Brazil. The potassium feldspar content was 94.5% by weight. Palm-sized field samples were pulverized in a jaw crusher and sieved to obtain particles smaller than 2 mm in size. Reagent-grade calcium oxide (CaO) was used as is.

[0081] The feed mixture (starting material) was obtained by dry grinding ultrapotassium syenite (<2 mm) to a particle size of 90-150 μm. Based on the assumption that there is no Si in CaO and no Ca in ultrapotassium syenite, CaO was added to the potassium feldspar-rich powder to achieve a nominal Ca:Si molar ratio of 0.3.

[0082] The hydrothermal reaction of the first step was studied using a customized fine sensor setup with a round-bottom flask (RBF) and a multi-fin aluminum heat exchanger for temperature control. Magnetic stirring was performed to ensure efficient mixing during the hydrothermal reaction.

[0083] The experiment for the second step was carried out in a Swagelok high-pressure cylinder with a reactor capacity of 150 ml and dimensions of 12.4, 5.08, and 0.24 cm in length (end to end), diameter, and thickness, respectively. The high-pressure cylinder was fixed in a horizontal position to provide uniform heating along the length of the cylinder, and the reactor temperature was measured at the center of the cylinder. An induction heating setting was used to heat the pressure cylinder. The pressure cylinder was located inside the induction coil. The induction power controller controlled the temperature using a Type K thermocouple inserted inside the pressure cylinder. The contents of the high-pressure cylinder were not mixed throughout this step.

[0084] Potassium (K + The availability of (K) was measured using a standard leaching test, in which 1 g of MPM was mixed with 100 g of 0.1 M nitric acid solution and stirred for 30 minutes. The solution was then filtered using Whatman filter paper, and the resulting leachate was extracted from the sample (K + The weight percentage of potassium was analyzed by ICP-MS (PerkinElmer NexION 300X). The amount of potassium extracted during the leaching test has been observed to be a good surrogate for the amount of conversion that occurred when comparing MPM to the starting material (supply material).

[0085] Example 1 In Example 1, approximately 52 g of the standard feedstock mixture was used for each experiment. Water was added to the RBF together with the feedstock in an L / S ratio of 4:1 and held at 95°C for 2 hours (Step 1). After this period, approximately 30 g of the resulting / intermediate slurry sample was then inserted into a Swagelok high-pressure cylinder, where the intermediate product was then heated to 220°C and held under the resulting pressure without stirring for a given amount of time (Step 2). Four different runs were performed, with the same Step 1 but varying the residence time for Step 2, while maintaining the pressure and temperature at set levels. After Step 2 was completed, the resulting slurry was extracted from the pressure vessel and dried in a laboratory oven at approximately 120°C and atmospheric pressure, after which only the dried MPM remained. The resulting MPM was then tested through a standard leaching test.

[0086] From the MPM sample held at 220°C for 5 minutes during the second step, 0.40 wt% K + However, it was extracted during the leaching test. From the MPM sample held at 220°C for 30 minutes during the second step, 0.75% by weight of K was extracted. + However, it was extracted during the leaching test. For the sample held at 220°C for 60 minutes during the second step, 1.11% by weight of K + However, it was extracted during the leaching test. From the MPM sample maintained at 220°C for 120 minutes during the second step, 1.75% by weight of K was extracted. + However, it was extracted during the leaching test. The results are summarized in Table I and Figure 3.

[0087] JPEG0007879171000001.jpg22125

[0088] While keeping the first step the same throughout the entire experiment, the increase in residence time during the second step resulted in a decrease in the K of the resulting MPM. + An increase in availability was observed.

[0089] Example 2 In Example 2, approximately 52 g of the standard feedstock mixture was used for each experiment. Water was added to the feedstock at a L / S ratio of 4:1 to the RBF and held at 95 °C for 2 hours (first step). After this period elapsed, a sample of approximately 30 g of the resulting / intermediate slurry was inserted into a Swagelok high-pressure cylinder where the intermediate product was then heated for 1 hour at various temperatures (second step). Four different runs were performed by varying the temperature and resulting pressure for the second while keeping the first step the same. After the second step was completed, the resulting slurry was extracted from the pressure vessel and dried in an experimental oven at approximately 120 °C and atmospheric pressure, after which only the dried MPM remained. The resulting MPM was then tested through a standard leaching test.

[0090] From the MPM sample held at 190 °C for 1 hour during the second step, 0.39 wt% of K + was extracted during the leaching test. From the MPM sample held at 220 °C for 1 hour during the second step, 1.11 wt% of K + was extracted during the leaching test. From the MPM sample held at 250 °C for 1 hour during the second step, 1.93 wt% of K + was extracted. From the MPM sample held at 280 °C for 1 hour during the second step, 2.25 wt% of K + was extracted during the leaching test. The results are summarized in Table II and Figure 4.

[0091] JPEG0007879171000002.jpg22125

[0092] While keeping the first step the same throughout the experiment, an increase in the temperature for the second step was observed to increase the K + availability of the resulting MPM.

[0093] Example 3 In Example 3, approximately 52 g of standard feedstock was used for each run. A total of six experiments were conducted, varying both the L:S ratio and the temperature of the second step. Water was added to the RBF along with the feedstock at three different L / S ratios, namely 2:1, 3:1, and 4:1, and held at 95°C for 2 hours (first step). After this period, the resulting slurry was then inserted into a Swagelok high-pressure cylinder, where the intermediate product was then heated and held at either 220°C or 250°C for 1 hour (second step). After the second step, the resulting slurry was extracted from the pressure vessel and dried in a laboratory oven at approximately 120°C and atmospheric pressure, after which only the dried MPM remained. The resulting MPM was then tested through a standard leaching test.

[0094] From the MPM sample, which was manufactured with a 2:1 L:S ratio and held at 220°C for 1 hour during the second step, 0.95 wt% K was obtained. + However, it was extracted during the leaching test. From the MPM sample prepared with a 2:1 L:S ratio and held at 250°C for 1 hour, 1.72% by weight of K was extracted. + However, it was extracted.

[0095] From the MPM sample, which was manufactured with an L:S ratio of 3:1 and held at 220°C for 1 hour during the second process, 1.07 wt% K was obtained. + However, it was extracted during the leaching test. From the MPM sample prepared with a 3:1 L:S ratio and held at 250°C for 1 hour during the second step, 1.87% by weight of K was extracted. + However, it was extracted during the leaching test.

[0096] From the MPM sample, which was manufactured with an L:S ratio of 4:1 and held at 220°C for 1 hour during the second process, 1.11 wt% K was obtained. + However, it was extracted during the leaching test. From the MPM sample prepared with a 4:1 L:S ratio and held at 250°C for 1 hour during the second step, 1.93% K was extracted. + However, it was extracted during the leaching test.

[0097] The results are summarized in Table III and Figure 5.

[0098] JPEG0007879171000003.jpg26144

[0099] It was observed that variations in the L:S ratio did not substantially affect the conversion efficiency of the feedstock, at least within these boundaries. Furthermore, as already observed above, the rise in temperature during the second process affected the resulting K of the MPM. + Availability was increased.

[0100] Example 4 In Example 4, the effect of temperature on the first step was also tested. Approximately 52 g of standard feed material was mixed with water in a 4:1 L:S ratio, stirred, and held at a fixed temperature for 5 hours. Four different temperatures, namely room temperature at 25°C, 30°C, 60°C, and 95°C, were tested to obtain four distinct intermediate materials. After 5 hours at each temperature, a standard leaching test was performed on each of the intermediate materials. The results are summarized in Table IV and Figure 6.

[0101] JPEG0007879171000004.jpg22125

[0102] Increasing the temperature used in the first step is the K of the intermediate product produced by the first step. + It was observed that this increased the availability of [the material].

[0103] Example 5 The impact on conversion within the first process was investigated by varying the duration of the first process up to a maximum of 320 hours. Standard feedstock was used, with an L:S ratio of 4:1, and maintained at a temperature of 90°C (after a 24-hour residence time, the temperature was reduced to 80°C to avoid excessive evaporation). The results are shown in Table V and Figure 7.

[0104] The results showed that increasing the residence time for the first process resulted in K in the intermediate material. + This indicates an increase in availability.

[0105] JPEG0007879171000005.jpg22144

[0106] Example 6 Mineralogy was determined by X-ray powder diffraction (XRPD), analyzing (i) standard feedstock; (ii) intermediate product after the first step carried out with stirring at 100°C for 30 minutes; and (iii) MPM produced after the second step of a two-step process in which the first step was carried out with stirring at 100°C for 300 minutes and the second step was carried out without stirring at 220°C for 30 minutes. Powder samples were backloaded onto a sample holder and placed in a diffractometer (Panalytical X'Pert MPD) using 45 kV and 40 mA CuKα radiation as the X-ray source. Once identified, the mineral phase was quantified via the internal standard method and Rietveld purification. The results are shown in Table VI.

[0107] TIFF0007879171000006.tif28166

[0108] By comparing the mineralogy of the intermediate product with that of the MPM in Table VI, it is clear that significant mineralogical changes occurred during the second step. However, by comparing the mineralogy of the intermediate product with that of the standard feedstock in Table VI, it is also clear that a certain level of change, demonstrated, for example by an increase in the amorphous phase, already occurs during the first step.

[0109] Other Embodiments While specific embodiments have been provided, this disclosure is not limited to such embodiments.

[0110] As an example, in some embodiments, the MPM may include at least one additional component. Examples of such materials include KCl (potassium rock salt phase), one or more micronutrients (e.g., nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and sulfur (S)), one or more micronutrients (e.g., boron (B), chlorine (Cl), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), and zinc (Zn)), and / or one or more other beneficial elements (e.g., sodium (Na), selenium (Se), silicon (Si), cobalt (Co), and vanadium (V)).

[0111] In general, at least one additional component can be introduced as part of any of the processes disclosed herein. In some embodiments, at least one additional component is added during the first step. In certain embodiments, at least one additional component is added after the second step. In some embodiments, at least one additional component is added during the intermediate step. In certain embodiments, at least one additional component is added after MPM formation, but before drying. In some embodiments, at least one additional component is added after drying.

[0112] In general, sources of additional components can be used in any suitable form. Examples of such forms include crystals, salts, powders, liquids (e.g., solutions), and / or slurries. An exemplary and non-exclusive list of source materials is as follows: Examples of phosphorus (P) sources include phosphate rocks (e.g., raw materials for phosphate fertilizer production), phosphoric acid (e.g., intermediate products from the phosphate fertilizer production chain), and monoammonium phosphate. Examples of nitrogen (N) sources include ammonia and urea. Examples of potassium (K) sources include KCl and potassium sulfate (SOP). Examples of magnesium (Mg) sources include magnesia and dolomite lime. Examples of sulfur (S) sources include gypsum, sulfur, and ammonium sulfate. Examples of calcium (Ca) sources include gypsum and dolomite lime. An example of copper (Cu) source is copper sulfate. Examples of boron (B) sources include borates, borax, and boric acid. An example of zinc (Zn) source is zinc sulfate. One example of a manganese (Mn) source is manganese sulfate. Additional suitable sources of these and other components are known.

[0113] In some embodiments, the MPM may have a cation exchange ratio of at least 10 mmol / kg and / or up to 2,000 mmol / kg.

[0114] In certain embodiments, K in the MPM + The percentage is between 5% and 55%.

[0115] In certain embodiments, the MPM may have a salinity index between 5% and 119%.

[0116] Specific aspects of reaction methods and materials relating to MPM formation are disclosed in U.S. Patent No. 9,340,465, U.S. Patent No. 10,800,712, and International Patent Application No. PCT / IB2021 / 051351. The disclosures of these documents are incorporated herein by reference. To the extent that the subject matter disclosed in these documents conflicts with the subject matter disclosed in this application, this application shall be relied upon to resolve such conflict.

Claims

1. a) Reacting the starting materials at a temperature of at least 30°C to a maximum of 100°C to form an intermediate product; and b) Reacting the intermediate product at a temperature of at least 180°C to a maximum of 400°C to form a multiphase material (MPM); and b) After that, dry the MPM at a temperature of at least 25°C to a maximum of 400°C. A method for producing a multiphase material (MPM), wherein the method produces an MPM and the starting material is: One or more potassium-skeletal silicates; and Alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, and alkaline earth metal carbonates, and one or more compounds selected from combinations thereof. Includes, The MPM comprises at least two phases selected from the group consisting of potassium feldspar phase, tobermorite phase, hydrogrossular phase, dicalcium silicate hydrate phase, and amorphous phase. This method uses MPM: To use as fertilizer; To be used for soil remediation; To be used for soil decontamination; To use in order to increase crop yield; or To be used to improve soil health and / or to improve soil fertility. Further including, method.

2. The method of claim 1, wherein step b) is carried out without stirring.

3. The method of claim 1 or 2, wherein a) is carried out at a temperature of at least 35°C or at least 40°C.

4. The method of claim 1 or 2, wherein a) is carried out at a maximum pressure of 2 atmospheres.

5. The method of claim 1 or 2, wherein b) is carried out at a pressure of at least 5 atmospheres.

6. The method of claim 1 or 2, further comprising heating to a temperature of at least 180°C between a) and b).

7. The method of claim 1 or 2, further comprising increasing the pressure between a) and b) from a maximum pressure of 2 atmospheres to a pressure of at least 5 atmospheres.

8. The method according to claim 1 or 2, wherein a) is carried out in a first reaction vessel, and b) is carried out in a second reaction vessel different from the first reaction vessel.

9. a) is carried out for at least 15 minutes, and / or a) will be implemented for a maximum of two weeks. The method according to claim 1 or 2.

10. b) is performed for at least one minute, and / or b) will be implemented for a maximum of 24 hours. The method according to claim 1 or 2.

11. a) is: a1) Reacting the starting materials at a first temperature of up to 50°C to form a first material; and a2) After a1), the first material is reacted at a second temperature higher than the first temperature to form an intermediate product. The method of claim 1 or 2, comprising:

12. The method of claim 11, wherein the second temperature is a maximum of 100°C.

13. The method of claim 11, wherein a1) is carried out at a temperature of at least 20°C.

14. The method of claim 1 or 2, wherein drying occurs at a pressure of at least 1 atmosphere and up to 100 atmospheres.

15. The method of claim 1 or 2, wherein one or more potassium skeleton silicates comprises at least one member selected from the group consisting of potassium feldspar, calcilite, nepheline, phlogopite, muscovite, biotite, trachyte, rhyolite, mica, hyperpotassium syenite, garnet, nepheline syenite, phonolite, phenite, aplite, and pegmatite.

16. The method of claim 1 or 2, wherein the MPM comprises a potassium feldspar phase in the range of 1% to 74.5% by weight, a tobermorite phase in the range of 0.1% to 55% by weight, a hydrogrossular phase in the range of 0.1% to 15% by weight, a dicalcium silicate hydrate phase in the range of 0% to 20% by weight, an amorphous phase in the range of 0% to 55% by weight, a potassium salt phase in the range of 0.1% to 99% by weight, and a minor component phase in the range of 0.1% to 20% by weight.

17. The method of claim 1 or 2, wherein b) is carried out at a temperature of at least 190°C, at least 200°C, at least 210°C, at least 220°C, at least 230°C or at least 240°C.

18. The method of claim 1 or 2, wherein b) is carried out at a temperature of up to 350°C, up to 300°C, or up to 290°C.

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