Multi-step method for producing multi-phase 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-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Application No. 63 / 214,958, filed June 25, 2021, the contents of which are incorporated herein by reference.

[0002] Field The present disclosure provides a multi-step method for producing a multi-phase material (MPM). [Background technology]

[0003] background A single-step process for producing MPMs using an autoclave is known. Summary of the Invention

[0004] overview The present 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 operational expenditures. 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 the use of an autoclave. For example, the first step can be carried out in a non-pressurized reaction vessel, which can reduce costs compared to processes that use an autoclave. Furthermore, the second step can be carried out in a relatively inexpensive pressurized reaction vessel (e.g., a pipe reactor). Furthermore, alternative pressurized reaction vessels, such as, for example, a pipe reactor, can allow for higher temperatures and resulting pressures compared to an autoclave.

[0005] Generally, the method includes at least two steps. In some embodiments, the first step is carried out at a relatively low temperature (e.g., up to 100° C.) and / or a relatively low pressure (e.g., up to 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, the method can include more than two steps. As an example, the method can include heating to an intermediate temperature (a temperature between the minimum and maximum 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 may be held for a desired period of time (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), before heating to a higher temperature (e.g., the temperature used in the second step). In general, 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 pressure of up to 2 atmospheres; and 2) a temperature of up to 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) of the conditions of the first step and one or more (e.g., all) of the conditions of the second step. For example, the temperature can be a smooth transition and / or the pressure transition 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.

[0006] Without being bound by theory, it is believed that the conditions of the first step may allow for good mass transfer of calcium ions, perhaps because calcium oxide (CaO) is more soluble under these conditions, which allows for an initial reaction between calcium and potassium feldspar to produce the intermediate product. Also, without being bound by theory, it is believed that one or more steps after the first step may allow for 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 calcium ion mass transfer and rate of MPM formation.

[0007] In one aspect, the disclosure provides a method of making an MPM comprising: a) reacting starting materials at a temperature of 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 aspect, the disclosure provides a method of making 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 aspect, the disclosure provides a method of making an MPM comprising: 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 aspect, the disclosure provides a method of 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 wherein the method produces an MPM.

[0011] In one aspect, the disclosure provides a method of producing an MPM comprising reacting starting materials at a temperature of 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 a temperature of up to 100°C (eg, at a temperature of up to 90°C, up to 80°C, up to 70°C, up to 60°C) and / or at a temperature of 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 of up to 400°C.

[0014] In some embodiments, a) can be carried out at a pressure of up to 2 atmospheres (eg, 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 (eg, 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 comprise 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 and b) may include heating to a second temperature, the intermediate temperature being between the first temperature and the second temperature.

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

[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 and b) may include using a second pressure, the intermediate pressure being 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 distinct from the first plurality of reaction vessels.

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

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

[0024] In certain embodiments, b) can include agitating the reaction product.

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

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

[0027] In some embodiments, b) can be carried out using a reaction vessel selected from the group including an autoclave, a pipe reactor, a three-phase gas-liquid-solid contractor, and a rotating drum.

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

[0029] In certain embodiments, b) can be performed for at least 1 minute (eg, at least 5 minutes) and / or up to 1 week (eg, up to 24 hours).

[0030] In certain embodiments, a) may include: a1) reacting starting materials at a first temperature of 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 is up to 100° C. a1) may be carried out at a temperature of up to 50° C. a2) may be carried out at a temperature of at least 75° C.

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

[0032] In certain embodiments, the starting material may include potassium skeletal silicate ore. The starting material may include at least one member selected from the group including, for example, K-feldspar, kalsilite, nepheline, phlogopite, muscovite, biotite, trachyte, rhyolite, mica, ultra-K-syenite, leucite, nepheline syenite, phonolite, fenite, aplite, and pegmatite. In some embodiments, the starting material may include K-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 an alkaline earth metal and an alkali metal. 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 an alkaline earth metal and an alkali metal. In certain embodiments, the starting material may include at least one oxide, hydroxide, and carbonate of an alkaline earth metal and an alkali metal. In some embodiments, the metal may include at least one member selected from the group including lithium (Li), sodium (Na), and potassium (K), beryllium (Be), magnesium (Mg), calcium (Ca), 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 provided in a single batch.

[0034] In certain embodiments, the starting materials are provided in a stepwise manner.

[0035] In some embodiments, at least one of the following is true: the starting material may include potassium framework silicate ore and CaO, with a molar ratio of Ca:Si between 0.05 and 4; the starting material may include potassium framework silicate ore and Ca(OH)2, with a molar ratio of Ca:Si between 0.05 and 4; and the starting material may include potassium framework silicate ore and CaCO3, with a molar ratio of Ca:Si 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, a source of macronutrients, a source of micronutrients, and a source of beneficial elements, for example, the at least one member may include 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 adding at least one member selected from the group including KCl, a source of macronutrients, a source of micronutrients, and a source of beneficial elements to the intermediate product prior to b), wherein the at least one member may include 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.

[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 comprising 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 include at least 1% by weight of a potassium feldspar phase, and / or up to 74.5% by weight of a potassium feldspar phase.

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

[0043] In some embodiments, the MPM may contain at least 0.1 wt.% hydrogrossular phase, and / or up to 15 wt.% 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 a dicalcium silicate hydrate phase.

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

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

[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 a minor component phase, and / or up to 20% by weight of a minor component phase.

[0048] In certain embodiments, the MPM has a Salinity Index of between 5% and 119%.

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

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

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

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

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

[0054] In certain embodiments, the compositions can be used as fertilizers, for soil remediation, for decontaminating soil, for increasing crop yields, for improving soil health, and / or for improving soil fertility. [Brief description of the drawings]

[0055] Illustrative embodiments of the present disclosure are provided below with reference to the drawings. [Figure 1] FIG. 1 illustrates one embodiment of the two-step process. [Diagram 2] FIG. 2 shows one embodiment of a process that includes more than two steps. [Diagram 3] FIG. 3 shows the experimental results when the residence time for the second step was changed (Example 1). [Figure 4] FIG. 4 shows the experimental results when the temperature for the second step was changed (Example 2). [Diagram 5] FIG. 5 shows the experimental results when varying the liquid to solid (L:S) ratio for the overall process and the temperature for the second step (Example 3). [Figure 6] FIG. 6 shows the experimental results when the temperature used in the first step was changed (Example 4). [Figure 7]FIG. 7 shows the results of an experiment in which the residence time used for the first step was varied (Example 6). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0056] Description of Illustrative Embodiments 1 illustrates generally one embodiment of a two-step process 100 for making an MPM. In a first step 102, starting materials are mixed in a first reaction vessel and reacted under a first set of conditions for a first period of time to form an intermediate product. In a second step 104, the intermediate product is placed in a second reaction vessel and heated under conditions to form the MPM.

[0057] Generally, the starting material includes one or more potassium framework 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, and then contacted with water. The starting material can be added via a continuous process or via a batch process. Contacting the mixture with water can be performed by any suitable method, such as by adding water to the mixture, or by adding the mixture to water, or by adding water and the mixture to a suitable reaction vessel sequentially or simultaneously (see discussion below). Generally, any suitable amount of water can be used. In some embodiments, a weight excess of water is used relative to the potassium framework silicate starting material.

[0058] In some embodiments, the potassium framework silicate can be potassium feldspar, kalsilite, nepheline, trachyte, rhyolite, ultrapotassium syenite, leucite, nepheline syenite, phononite, fenite, aplite, or pegmatite. Combinations of such potassium framework silicates can be used.

[0059] In some embodiments, the one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, comprise calcium oxide, calcium hydroxide, or mixtures thereof. In some embodiments, the one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, comprise calcium hydroxide. In some embodiments, the one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, comprise calcium oxide. In certain embodiments, the one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and combinations thereof, comprise lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium, and / or cesium hydroxide. In some embodiments, the 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 calcium-containing materials (i.e., CaO, Ca(OH)2, CaCO3, (Ca,Mg)CO3, and combinations thereof) to silicon-containing materials (i.e., potassium framework silicates) can be used to adjust the mineralogy, extraction, 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 at most 4.

[0061] As noted above, the starting material may be in the form of coarser and / or finer particles. The particles may be formed by any suitable process, such as, for example, co-grinding or comminuting separately, using methods known in the art, such as crushing, milling the dried or slurried materials, for example, using jaw crushers, gyratory crushers, cone crushers, ball mills, pulverizing mills, rod mills, etc. The resulting mixture may 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 a temperature of 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 ranges therebetween.

[0063] Generally, the first step 102 is carried out at a pressure of 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 ranges therebetween.

[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 ranges therebetween. However, in certain embodiments, the period used for the first step may vary. As an example, when using evaporation ponds (e.g., in a relatively hot and dry environment such as a desert), the first step may be carried out for more than 2 weeks (e.g., at least 1 month).

[0065] In general, the first step 102 can be carried out with or without agitation. In embodiments that include agitation, any suitable agitation mechanism can be used. Illustrative examples of agitation 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 closed tanks, open tanks, containment vessels, open evaporation ponds, tubular vessels such as pipes and rotating drums, rotating disks, solid-liquid contractors such as solid-liquid fluidized beds, and hydrocyclones.

[0067] In certain embodiments, the first step 102 may include two or more sub-steps. A sub-step may include reacting starting materials at a first temperature to form a first material, and then heating the first material to react into 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 involves heating to convert the intermediate material to an MPM. In some embodiments, the second step 104 involves using a temperature 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 ranges therebetween.

[0069] Generally, the second step 104 is 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 up to 300 atmospheres (e.g., up to 200 atmospheres, up to 100 atmospheres, up to 75 atmospheres), including ranges therebetween.

[0070] Typically, the second step 104 is performed 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 ranges therebetween.

[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 be different from the 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 of the reaction vessels used in the second step 104 may be different from the one or more reaction vessels used in the first step 102. Any reaction vessel suitable for the conditions used can be implemented 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] 2 shows a method 200 that includes a first step 202 (e.g., similar to that described above with respect to step 102) and a second step 204 (e.g., similar to that 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 holding this intermediate temperature for a period of time. In some embodiments, step 203 includes holding 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 held for a desired period of time (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 performed using the same or similar pressure conditions as used in step 204. In certain embodiments, step 203 is performed 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 performed with or without stirring. Step 203 is typically performed using the same reaction vessel(s) used in step 204, although using one or more different reaction vessels for step 203 compared to step 204 is an option.

[0074] While FIG. 2 shows a single intermediate step 203 between the first step 202 and the second step 204, there may be a transition 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 (e.g., more than two intermediate steps, more than five intermediate steps, more than ten intermediate steps, more than one hundred intermediate steps) between the first step 202 and the second step 204. 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 a further example, in some embodiments, there is a transition between both: 1) a temperature of at least 20° C. and a pressure of up to 2 atmospheres; and 2) a temperature of up to 400° C. and a pressure of up to 300 atmospheres. In such embodiments, there is more than one intermediate temperature between the first step and the second step, and there is more than one intermediate pressure between the first step and the second step. In some embodiments, the transition between the first step and the second step is a smooth transition between one or more (e.g., all) of the conditions of the first step and one or more (e.g., all) of the conditions of the second step. For example, the temperature may be a smooth transition and / or the pressure transition 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 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 minimum temperature of the intermediate step between steps 202 and 204 is higher than the temperature used in the first step 202 and the maximum temperature of the intermediate step is lower than the temperature used in the second step 204 .Generally, the minimum pressure of the intermediate step between steps 202 and 204 is higher than the pressure used in the first step 202 and the maximum pressure of the intermediate step is lower than the pressure used in the second step 204 .

[0075] Generally, after formation of the MPM according to the steps described above, a drying step is carried out. In some embodiments, the drying step can be carried out under ambient temperature (e.g., by evaporating the supernatant water). In certain embodiments, the drying step is carried out at at least 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 ranges therebetween. In some embodiments, the 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 ranges therebetween. In some embodiments, the drying is carried out under an inert atmosphere or under a reactive atmosphere. The inert atmosphere can 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. In general, the drying step can occur with or without agitation. In certain embodiments, the drying step is carried out for a period of 1 minute to 2 days (eg, 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 a K-feldspar phase, a tobermorite phase, a hydrogrossular phase, a dicalcium silicate hydrate phase, and an amorphous phase. In some embodiments, the MPM comprises a K-feldspar phase, a tobermorite phase, a hydrogrossular phase, a dicalcium silicate hydrate phase, and an amorphous phase. In certain embodiments, the MPM comprises at least 1 wt.% K-feldspar phase and / or up to 74.5 wt.% K-feldspar phase. In some embodiments, the MPM comprises at least 0.1 wt% tobermorite phase and / or up to 55 wt% 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 comprises at least 0.1 wt% hydrogrossular phase and / or up to 15 wt% hydrogrossular phase (e.g., 0.1 wt% to 12 wt%). In certain embodiments, the MPM comprises dicalcium silicate hydrate phase in an amount of up to 20 wt% (e.g., up to 10 wt%, up to 15 wt%, up to 12 wt%). In some embodiments, the MPM comprises amorphous phase in an amount of up to 55 wt% (e.g., up to 45 wt%). In certain embodiments, the MPM further comprises minor component phases (e.g., in an amount of at least 0.1% and / or up to 20% by weight). In some embodiments, the MPM comprises a K-feldspar phase in the range between 1% and 74.5% by weight, a tobermorite phase in the range between 0.1% and 55% by weight, a hydrogrossular phase in the range between 0.1% and 15% by weight, a dicalcium silicate hydrate phase in the range between 0% and 20% by weight, an amorphous phase in the range between 0.1% and 55% by weight, a K-rock salt phase in the range between 0.1% and 99% by weight, and minor component phases in the range between 0.1% and 20% by weight. In some embodiments, the MPM comprises 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] Generally, 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] Experiments were conducted to evaluate the effect of residence time for both the first and second steps, the effect of temperature for both the first and second steps, and the liquid to solid (L:S) ratio when producing MPM.

[0080] The ultrapotassium syenite used in the examples was obtained from the Triunfo batholith, located in the state of Pernambuco, Brazil. The potassium feldspar content was 94.5% by weight. A palm-sized field sample was pulverized in a jaw crusher and sieved to obtain particles with a size of less than 2 mm. Reagent grade calcium oxide (CaO) was used as received.

[0081] The feed mixture (starting material) was obtained by dry grinding ultrapotassium syenite (<2 mm) to P90-150 μm. Based on the assumption that there is no Si in CaO and no Ca in ultrapotassium syenite, CaO was added to the K-feldspar-rich powder to achieve a nominal Ca:Si molar ratio of 0.3.

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

[0083] The second step experiments were carried out in a Swagelok high pressure cylinder with a reactor volume of 150 ml and dimensions of length (end to end), diameter and thickness of 12.4, 5.08 and 0.24 cm, 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 setup was used to heat the pressure cylinder. The pressure cylinder was inside the induction coil. The controller of the induction power supply controlled the temperature using a type K thermocouple inserted inside the pressure cylinder. The contents of the high pressure cylinder did not mix throughout the process.

[0084] Potassium (K + Measurement of the availability of MPM was performed in 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 amount of potassium extracted during the leaching tests has been observed to be a good proxy for the amount of conversion that has occurred when comparing the MPM to the starting material (feedstock).

[0085] Example 1 In Example 1, about 52 g of the standard feed mixture was used for each experiment. Water was added to the RBF with the feedstock at a 4:1 L / S ratio and held at 95° C. for 2 hours (first step). After this period, about 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 (second step). Four different runs were performed with the same first step, while the pressure and temperature were held at set levels, but by varying the residence time for the second step. After the second step was over, the resulting slurry was extracted from the pressure vessel and dried in a laboratory oven at about 120° C. and atmospheric pressure, after which only the dried MPM remained. The resulting MPM was then tested through a standard leaching test.

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

[0087] JPEG2024525419000002.jpg22125

[0088] While the first step was kept the same throughout the experiment, an increase in the residence time during the second step increased the K + It was observed that this increased the availability of

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

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

[0091] JPEG2024525419000003.jpg22125

[0092] While the first step was kept the same throughout the experiment, an increase in temperature for the second step was observed to increase the K + It was observed that this increased the availability of

[0093] Example 3 In Example 3, about 52 g of standard feedstock was used for each run. Both the L:S ratio and the temperature of the second step were varied, resulting in a total of six experiments. 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 had elapsed, 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 was over, the resulting slurry was extracted from the pressure vessel and dried in a laboratory oven at about 120°C and atmospheric pressure, after which only the dried MPM remained. The resulting MPM was then tested through a standard leaching test.

[0094] The MPM sample produced with a 2:1 L:S ratio and held at 220 °C for 1 h during the second step contained 0.95 wt.% K. + was extracted during the leaching test. From the MPM sample made with a 2:1 L:S ratio and held at 250 °C for 1 h, 1.72 wt.% K was extracted. + was extracted.

[0095] The MPM sample produced with a 3:1 L:S ratio and held at 220°C for 1 hour during the second step contained 1.07 wt% K. + was extracted during the leaching test. The MPM sample produced with a 3:1 L:S ratio and held at 250°C for 1 hour during the second step contained 1.87 wt.% K. + was extracted during the leaching test.

[0096] The MPM sample produced with a 4:1 L:S ratio and held at 220°C for 1 hour during the second step contained 1.11 wt% K. + was extracted during the leaching test. The MPM sample produced with a 4:1 L:S ratio and held at 250°C for 1 hour during the second step contained 1.93% K. + was extracted during the leaching test.

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

[0098] JPEG2024525419000004.jpg26144

[0099] It has been observed that variation in the L:S ratio, at least within these bounds, does not substantially affect the conversion efficiency of the feedstock. Furthermore, and as already observed above, an increase in temperature during the second step does not significantly affect the K + Increased availability.

[0100] Example 4 In Example 4, the effect of temperature on the first step was also tested. Approximately 52 g of standard feedstock was mixed with water in a 4:1 L:S ratio, stirred and held at a fixed temperature for 5 hours. Four different temperatures were tested, namely room temperature @ 25°C, 30°C, 60°C and 95°C, thereby providing four respective intermediate materials. After the five hours had elapsed 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] JPEG2024525419000005.jpg22125

[0102] Increasing the temperature used for the first step increases the K + It was observed that the β-amyloid ions increased the availability of

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

[0104] The results show that increasing the residence time for the first step reduces the K + This shows that it increases the availability of

[0105] JPEG2024525419000006.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 at 100°C for 30 minutes with stirring; and (iii) MPM produced after the second step of a two-step process where the first step is carried out at 100°C for 300 minutes with stirring and the second step is carried out at 220°C for 30 minutes without stirring. Powder samples were backloaded onto a sample holder and placed in a diffractometer (Panalytical X'Pert MPD) using CuKα radiation at 45 kV and 40 mA as the X-ray source. Once identified, the mineral phases were quantified via internal standard method and Rietveld refinement. The results are shown in Table VI.

[0107] TIFF2024525419000007.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 have 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 already occurs during the first step, as evidenced, for example, by an increase in the amorphous phase.

[0109] Other embodiments Although specific embodiments have been provided, the present 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 (potash 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 an 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, the sources of the 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 illustrative and non-limiting list of source materials is as follows: Examples of phosphorus (P) sources include phosphate rock (e.g., feedstock 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 sulfate of potash (SOP). Examples of magnesium (Mg) sources include magnesia and dolomitic lime. Examples of sulfur (S) sources include gypsum, sulfur and ammonium sulfate. Examples of calcium (Ca) sources include gypsum and dolomitic lime. An example of a copper (Cu) source is copper sulfate. Examples of boron (B) sources include borates, borax and boric acid. An example of a zinc (Zn) source is zinc sulfate. An example of a source of manganese (Mn) is manganese sulfate. Additional suitable sources of these and other components are known.

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

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

[0115] In certain embodiments, the MPM may have a Salinity Index of between 5% and 119%.

[0116] Certain aspects of reaction methods and materials for forming MPMs 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 subject matter disclosed in these documents conflicts with subject matter disclosed in this application, this application shall be relied upon to resolve such conflict.

Claims

1. a) reacting starting materials at a temperature of up to 100 °C to form an intermediate product; and b) reacting the intermediate product at a temperature of at least 180 °C A method for producing a multiphase material (MPM), the method producing an MPM and the starting materials being: one or more potassium framework silicates; and one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, and alkaline earth metal carbonates, and combinations thereof A method.

2. a) reacting starting materials at a pressure of up to 2 bar to form an intermediate product; and b) reacting the intermediate product at a pressure of at least 5 bar A method for producing a multiphase material (MPM), the method producing an MPM and the starting materials being: one or more potassium framework silicates; and one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, and alkaline earth metal carbonates, and combinations thereof A method.

3. a) reacting starting materials to form an intermediate product; and b) reacting the intermediate product without stirring A method for producing a multiphase material (MPM), the method producing an MPM and the starting materials being: one or more potassium framework silicates; and one or more compounds selected from alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, and alkaline earth metal carbonates, and combinations thereof A method. Method according to any one of claims 1 to 3, wherein at least one of the following applies: a) is carried out at a temperature of at most 100 °C and / or at least 20 °C; b) is carried out at a temperature of at least 180 °C; a) is carried out at a pressure of at most 2 bar; and b) is carried out at a pressure of at least 5 bar and / or at most 300 bar. Claim 5 Method according to any one of claims 1 to 3, further comprising heating to a temperature of at least 180 °C between a) and b). Claim 6 Method according to any one of claims 1 to 3, further comprising heating to an intermediate temperature between a) and b), wherein: a) comprises heating to a first temperature; b) comprises heating to a second temperature; and the intermediate temperature is between the first temperature and the second temperature. Method according to any one of claims 1 to 3. Claim 7 Method according to any one of claims 1 to 3, further comprising increasing the pressure from a pressure of at most 2 bar to a pressure of at least 5 bar between a) and b). Claim 8 Method according to any one of claims 1 to 3, further comprising increasing the pressure to an intermediate pressure between a) and b), wherein: a) comprises using a first pressure; b) comprises using a second pressure; and the intermediate pressure is between the first pressure and the second pressure. Method according to any one of claims 1 to 3. Claim 9 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, or a) is carried out in a first plurality of reaction vessels and b) is different from the first plurality of reaction vessels. The method according to any one of claims 1 to 3, which is carried out in a plurality of reaction vessels of 2. The method according to any one of claims 1 to 3.

10. a) includes stirring the starting material, or a) does not include stirring the starting material, The method according to any one of claims 1 to 3.

11. b) includes stirring the reaction product, or b) does not include stirring the reaction product, The method according to any one of claims 1 to 3.

12. a) is carried out using a reaction vessel selected from the group consisting of a closed tank, an open tank, a storage container, an open evaporation pond, a tubular container, a rotating disk, a solid-liquid contractor, and a liquid cyclone, and / or b) is carried out using a reaction vessel selected from the group consisting of an autoclave, a pipe reactor, a three-phase gas-liquid-solid contractor, and a rotating drum, The method according to any one of claims 1 to 3.

13. a) is carried out for at least 15 minutes, and / or a) is carried out for a maximum of two weeks, The method according to any one of claims 1 to 3.

14. b) is carried out for at least 1 minute, and / or b) is carried out for a maximum of one week, The method according to any one of claims 1 to 3.

15. a) is: a1) reacting the starting material at a first temperature of 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 method according to any one of claims 1 to 3, comprising.

16. The method according to any one of claims 1 to 3, further comprising drying the product of b) after b).

17. One or more potassium framework silicates include at least one member selected from the group consisting of orthoclase, wollastonite, nepheline, phlogopite, muscovite, biotite, trachyte, rhyolite, mica, ultra-potassic diorite, leucite, nepheline syenite, phonolite, feniite, aplite and pegmatite, and / or The metal includes at least one member selected from the group consisting of lithium (Li), sodium (Na), potassium (K), beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr). The method according to any one of claims 1 to 3.

18. The method according to any one of claims 1 to 3, wherein at least one of the following applies: The starting material contains potassium framework silicate ore and CaO in a Ca:Si molar ratio between 0.05 and 4; The starting material contains potassium framework silicate ore and Ca(OH) ２ in a Ca:Si molar ratio between 0.05 and 4; and The starting material contains potassium framework silicate ore and CaCO ３ in a Ca:Si molar ratio between 0.05 and 4.

19. The method according to any one of claims 1 to 3, wherein the starting material contains at least one member selected from the group consisting of KCl, a source of macronutrients, a source of micronutrients and a source of beneficial elements.

20. The method according to any one of claims 1 to 3, wherein the MPM contains at least two phases selected from the group consisting of orthoclase phase, tobermorite phase, hydrogrossular phase, dicalcium silicate hydrate phase and amorphous phase.

21. The method according to any one of claims 1 to 3, wherein the MPM comprises a potassium feldspar phase in the range between 1 wt% and 74.5 wt%, a tobermorite phase in the range between 0.1 wt% and 55 wt%, a hydrogrossular phase in the range between 0.1 wt% and 15 wt%, a dicalcium silicate hydrate phase in the range between 0 wt% and 20 wt%, an amorphous phase in the range between 0 wt% and 55 wt%, a potassium rock salt phase in the range between 0.1 wt% and 99 wt% and a minor component phase in the range between 0.1 wt% and 20 wt%.

22. The method according to any one of claims 1 to 3, further comprising using the composition as a fertilizer, using it for soil remediation, using it for soil decontamination, using it to increase crop yield, using it to improve soil health, and / or using it to improve soil fertility.

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