Process and apparatus for manufacture of calcined compounds for the production of calcined products

Abstract

A process for producing a highly calcined and uniformly calcined product from a feedstock. The process comprising the steps of grinding the feedstock to powder, preheating the powder, and calcining the powder in a reactor plant that comprises a number of reactor segments in which a flash calciner is used in each progressive reactor segment to incrementally react the powder by raising the temperature in each segment. The last segment may be a high-temperature reactor that has a controlled residence time and temperature that may allow controlled finishing of the calcination process to achieve a desired degree of calcination and sintering of the product; and cooling of the product.

Claims

1. A process for producing a calcined product from a feedstock, the process comprising: grinding the feedstock to a powder; preheating the powder; calcining the powder in a reactor plant that comprises a plurality of reactor segments each comprising a flash calciner to incrementally react the powder in a calcination process by raising the temperature in each segment, wherein the feedstock comprises a carbon-containing compound, and wherein the plurality of reactor segments is indirectly heated such that carbon dioxide liberated in the indirectly heated plurality of reactor segments is not mixed with flue gas, so as to enable carbon capture; wherein a final reactor segment is a high-temperature reactor having a controlled residence time and temperature to allow controlled finishing of the calcination process to achieve a selected degree of calcination and sintering of the product; and cooling the product.

2. The process of claim 1, wherein the final reactor segment comprises a circulating fluidized bed reactor.

3. The process of claim 2, wherein the circulating fluidized bed reactor is directly heated by a heating gas, and an exhaust gas of the circulating fluidized bed is separately treated from exhaust gases of reactors in the earlier reactor segments.

4. The process of claim 1, wherein the plurality of reactor segments comprises at least one intermediate reactor segment externally heated using a gas stream derived from a combustion process.

5. The process of claim 1, wherein the reactor segments are electrically powered.

6. The process of claim 1, wherein the reactor segments are positioned in a tower configuration in which the calcination process proceeds from the top to the bottom.

7. The process of claim 1, wherein at least one gas selected from the group consisting of an inert gas and a reducing gas is used to entrain solids in the reactor plant without mixing with a flue gas.

8. The process of claim 1, wherein grinding the feedstock to a powder comprises forming a powder having a diameter of less than or equal to 100 microns.

9. The process of claim 1, wherein the calcination process results in evolution of gases and further comprising removing at least a portion of the gases at an end of each reactor segment to facilitate progress of the calcination process in subsequent segments.

10. The process of claim 9, wherein the gases removed at the end of reactor segment are ducted upward and combined such that that the gases are progressively cooled by downflowing reactants.

11. The process of claim 1, wherein the feedstock is a carbonate selected from the group consisting of magnesite, dolomite, and limestone minerals and mixtures thereof.

12. The process of claim 11, wherein the feedstock is a dolomitic magnesite mineral of a composition suitable for production of magnesium metal or refractory materials.

13. The process of claim 1, further comprising producing a porous catalyst substrate by calcination of volatiles to control a pore size distribution of the porous catalyst substrate through controlled sintering.

14. The process of claim 11, wherein the feedstock comprises at least one hydrated mineral.

15. The process of claim 14, wherein the at least one hydrated mineral comprises a synthetic carbonate compound.

16. The process of claim 13, wherein the volatiles comprise at least one material selected from the group consisting of hydrated water, carbon dioxide, ammonia and organic materials.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Embodiments of the disclosure will be better understood and readily apparent to one of ordinary skill in the art from the following description, by way of example only, and in conjunction with the drawings, in which:

(2) FIG. 1 shows a schematic drawing of a process for production of dolime and a relatively pure CO.sub.2 stream from reactors according to a first embodiment.

(3) FIG. 2 illustrates an embodiment of the flash calciner reactor of FIG. 1.

DETAILED DESCRIPTION

(4) A first preferred embodiment of the present disclosure is described is for the specific application for the production of dolime from dolomite for magnesium production using indirect heating from a combustion process. This calcined product may have a specification for the maximum carbon content that is allowable in the furnace that vaporizes the magnesium, and a desirable requirement that the product has as high a surface area as possible to optimize the solid-state reaction between the dolime and the ferrosilicon in the furnace. This is a specific example or embodiment of a general method in which the calcined product must meet requirements of both reactivity and calcination.

(5) The dolime production process can be described by consideration of the process flow of FIG. 1. In this embodiment, that carbonate is dolomite with an appropriate magnesium to calcium ratio to optimize the production of magnesium metal using ferrosilicon. Such a feedstock may include brucite, Mg(OH).sub.2, and mixtures of pure dolomite MgCO.sub.3.CaCO.sub.3 and magnesite MgCO.sub.3, to achieve the desired ratio. The described process may be adapted to a device, method or system to achieve the same or similar outcomes or results.

(6) A suitable pre-heater and flash calciner reactor is of the type as described by Dr. Mark Sceats in published PCT Patent Application No. WO 2012/145802, which is incorporated herein by reference, may be suitable for an embodiment that uses combustion to supply the calcination energy. In that reactor, the separation of the heating gas from the calcination process gas this is achieved using indirect heating from the heating gas. This may be achieved using a metal or ceramic wall between the two flows. The heating gas and the process streams are in counterflow, such that such that the energy efficiency is high, in the same way that counterflow heat exchangers have a high energy efficiency. The solids fall under gravity and are entrained by the process gas steam, while the heating gas rises. The products have a high surface area because the residence time of the mineral is short to achieve the preferable counterflow.

(7) The residence time in the reactor of FIG. 2 of the above-mentioned document is determined by the entrainment of the solids in the gas, and the large amounts of CO.sub.2 produced in the reactor is such that the residence time cannot be readily increased in this reactor. In practice, the short residence time in this reactor is such that the residual amount of CO.sub.2 in the calcined product is in the range of 2%-5%. This product does not meet the specification for use in the production of magnesium.

(8) In this first preferred embodiment and as depicted in FIG. 1, the reactor comprises three reactor segments, in which the low and intermediate temperature segments are based on indirect counterflow processing, and the high temperature polishing reactor is a conventional direct mixing reactor typical of conventional flash calciners. The use of two indirect counter flow reactors is to increase the residence time of the solids, because the CO.sub.2 is released in two separate processes. The low temperature process is the calcination of magnesium hydroxide and magnesium carbonate, in magnesite or dolomite, which occurs in the range of below 750 C., while the intermediate temperature process is the calcination of the calcium carbonate, which occurs in the range of 800 C.-900 C. If the CO.sub.2 from the calcination of magnesium is not removed, the partial pressure of CO.sub.2 is sufficiently high that the reaction of the calcium site does not take place until the temperature of the heated solids is such that equilibrium partial pressure exceeds the CO.sub.2 pressure, namely about 900 C. The release of CO.sub.2 then occurs rapidly and the process becomes difficult to control. Most importantly, the combination of the two CO.sub.2 gas streams is such that entrainment of the solids by the gas is such that the residence time of the solids is low.

(9) In this embodiment, the plant for the production of the dolime for magnesium production comprises a crushing and grinding plant 100 which is adapted to grind feedstock into a powder, a calciner tower 102 and a CO.sub.2 processing plant 103. The calciner tower 102 is a structure that comprises a preheater reactor segment 110 in which the powder is preheated and the brucite Mg(OH).sub.2 is calcined to MgO; a low temperature flash calciner 111 using indirect heating from a heating gas produced in the first combustor 112 in which the magnesium carbonate, as the mineral component magnesite MgCO.sub.3 and the dolomite MgCO.sub.3.CaCO.sub.3, is calcined to magnesia MgO; a first solids gas separator 113 in which the partially processed powder is separated from the CO.sub.2 and steam; an intermediate temperature flash calciner 114 using indirect heating from a second combustor 115 in which the powder is processed such that any residual carbonate from the magnesium carbonate is calcined and the calcination of the calcium carbonate from the dolomite is substantially complete; a second solids gas separator 116 in which the substantially calcined power is separated from the CO.sub.2; a high temperature flash calciner 114 using direct heating from a third combustor 118 in which the degree of calcination of the powder is reduced to the specification required by control of the temperature and residence time; and a solids cooler 119 in which the product is cooled for storage and, for briquette production.

(10) The raw dolomite rock 200 is crushed and ground in the crushing and grinding plant 100. In this plant 100, moisture (not shown in FIG. 1) is removed by using the flue gas streams 246 and 247 from the calciner tower 102. The exhaust 248 from the plant 100 is fed into a filter (not shown) to remove fines and is exhausted in stack or calcine tower 102. The dolomite is ground to particles, preferably, of less than 100 microns diameter and, more preferably, to less than 50 microns diameter. The ground, substantially dry dolomite 201 is transported to the calciner tower 102 where it is processed to dolime.

(11) In this process, the dolomite 201 is heated in a preheater segment 110 to a temperature of about 600 C., which marks the onset of the calcination reaction that removes CO.sub.2 from the magnesium carbonate, MgCO.sub.3 sites in the mineral powder. During pre-heating, steam is liberated from any excess moisture from brucite, Mg(OH).sub.2 in the mineral powder. The steam entrains with the powder in the preheater 110. Stream 202 comprises the partly processed mineral (MgCO.sub.3).sub.x.(CaCO.sub.3).sub.y.(MgO).sub.z. and the steam. The details of the preheater segment 110 are described below. The stream 202 heated intermediate is injected into the flash calciner segment 111. This flash calciner 111 uses indirect heating to ensure that the carbon dioxide liberated during calcination does not mix with the heating gases used to provide the energy of the reaction. A suitable flash calciner is of the type described by Sceats, for example, in published PCT Patent Application No. WO 2012/145802, incorporated herein by reference. A schematic illustration of an example flash calciner reactor is illustrated in FIG. 2 hereof. As the powder and gas in stream 202 falls through the reactor 117, they are heated in the range of 650 C.-750 C. by the heating gas streams 242 and 244, externally applied. At this temperature, the decarbonation of the magnesium occurs to give an exhaust stream 203 comprising the intermediate processed powder semidolime (MgO).sub.x+z.(CaCO.sub.3).sub.y and a gas of CO.sub.2 and steam. The calcination of the magnesium is substantially complete. The stream 203 enters the first solids gas separator 113, in which the solids 204 are separated and flow into an intermediate temperature flash calciner 114. The gas stream is exhausted into a central tube (not shown in FIG. 1) that transports the gas to an exhaust at the top of the reactor as stream 213 and is cooled in the preheater 110. This stream also contains the CO.sub.2 stream from the intermediate temperature flash calciner 114 described below. The cooled CO.sub.2 stream 214 from the preheater 110 is fed into the CO.sub.2 Processing plant 103 where it is dewatered, with a stream of water 211, compressed or liquefied for sequestration as 215. The partially hot semidolime stream 203 is substantially completely calcined in the intermediate flash calciner 114 by a heating gas stream 241, externally provided. A process steam 205 contains the calcined powder and the CO.sub.2, and this stream and these are separated in the second solid gas separator 116 to give a substantially calcined dolime stream 206 and a CO.sub.2 stream 210. The CO.sub.2 stream 210 is exhausted into a central tube and is exhausted as stream 211. The powder 206 is (MgO).sub.x+z.(CaO).sub.yv.(CaCO.sub.3).sub.v, with v<<y, and is metered into the high-temperature flash calciner 114, which is directly heated by heating gas 240 from the third combustor 118. In reactor 117, the excess carbonate is reduced from v to w to give (MgO).sub.x+z.(CaO).sub.yw.(CaCO.sub.3).sub.w, where w is sufficiently low that the product 207 meets the specifications. The vw CO.sub.2 is mixed with the heating gas as stream 243, and is cooled in the preheater 110 to give stream 244 which is used to dry the ground dolomite. The design of this reactor 117 is a fluidized bed in which the temperature of the product and the exhaust gas can exceed 1200 C. The residence time and temperature are controlled such that the desired degree of residual carbonate w is obtained. The mass flow of heating gas 240 is relatively small compared to those from the other combustors because the energy required to calcine the residual CaCO.sub.3 is small. This stream (heating gas 240) may be a slip stream from the other combustors. The hot calcined product 207 is cooled in the solids cooler 119, and this product is provided to the briquetting plant. Briquetting must be conducted in an inert gas to prevent recarbonation from CO.sub.2 in the atmosphere.

(12) The combustors 112, 115, 118 use cold, sub-stoichiometric primary air streams 224, 225 and 226 to transport the fuels 230, 231 and 232 into the combustors, where they are combusted with preheated air streams from the preheater 110 and solids cooler segments (not shown). The preheater 110 heats the air stream 227, and the heated air is split as streams 228 and 229 to the first and second combustors 112 and 115, respectively. The solids cooler (not shown) provides heat to air stream 220 for the provision of heated air in streams 221 and 222 for the third and second combustors 118 and 115, respectively.

(13) The preferred design of the preheater 110 and solids cooler are based on the following principles. Firstly, flows that are dominantly powders are restricted to vertical pipes that have diameters that are wide enough to prevent blocking, namely about 100 mm or more and the flow is downwards. There is an array of such pipes to manage the flows, and the flows are such that the powders are entrained in gas in a dilute flow. Where appropriate, steam is used to promote such flows. In this embodiment, in the preheater 110, the solid flow is the feed 201, and in the solids cooler 119, the solids flow is the product 207. Secondly, gas streams that contain minor amounts of process flow solids are also ducted through pipes, and in this embodiment such flows are upwards and forced by the gas streams. In this embodiment, in the preheater 110, the flows that contain some powders are the streams 243 and 213. It is preferable that these streams carry as small as possible solids, and where practical, there may be cyclones, including in-line cyclones, (not shown) that remove a large proportion of the solids and direct that flow back into the solids streams. Third, pure gas streams, such as air or heating gas are directed through the systems in a cross-flow pattern through horizontal ducts with a duct width chosen to give a gas velocity that is sufficiently high to achieve efficient heat transfer to or from the pipe walls. The gas streams move from one horizontal duct to another through shafts. In the solids cooler 119, the ducted gas stream is the air 220, and in the preheater 110 the ducted gases are the air 227 and the heating gas 245. Fourth, the heat flows are such that the ducted streams of gases are injected into the segments such that the vertical flow is a counterflow to the solids flows. Thus, in the preheater 110, the top of the preheater 110 is colder than the base, so the cool streams, as inputs or outputs are at the top and all the hot streams are at the base. Thus, streams 227 (in), 201 (in), 214 (out) and 247 (out) are at the top, and are cooler than the respective streams 228 (out), 202 (out), 213 (in) and 243 (in) at the base. In the solids cooler 119, the hot streams 207 (in), 221 (out), 222 (out), and 223 (out) are at the top, while the cool streams 208 (out) and 220 (in) are at the base. Using these principles, these segments may have a high thermal efficiency, and are compact.

(14) The preferred design of the flash calciners 111 and 114 are such that the CO.sub.2 streams from the respective gas solids separators 113 and 116 are ducted back through the reactors in a central tube. This aspect is a preferred embodiment in WO 2012/145802, and allows the reactors to be compact. The flows in that central tube are preferably in a vortex motion induced by the shape and orientation of the pipes in the preheater 110, and by deflector plates of the streams 203 and 205 entering the gas solids separators 113 and 116. This motion deflects the particles onto the wall of the central tube, and the particles flow down the walls into the gas solids separators 113 and 116. In effect, the tube is part of the design for the gas solids separators 113 and 116. The walls of the central tube shown in FIG. 2 are heated by the radiation from the reactor tube walls and the CO.sub.2 gas streams, and this assists the efficiency of the calcination processes in the reactor annuli.

(15) The sequence of the three reactors enables the product to meet the desired specifications of the product degree of calcination. The amount of CO.sub.2 that is captured in the first reactor represents about 50% of the total carbon input, the amount of CO.sub.2 that is captured in the second reactor amounts to about 45%, and the amount of CO.sub.2 that is discharged into the flue gas is about 5%. In this case, the capture efficiency of the system is 95%. The control of the residence time and temperature in the third reactor is important because the calcined particles rapidly sinter at high temperatures, and the consequential reduction of the surface area lowers the reactivity of the particles. In the case of magnesium production, on the one hand, the extent of sintering lowers the reaction rate with the ferrosilicon in the heated briquette, and on the other hand, the longer the sintering, the greater the degree of calcination, and the less carbon is introduced into the magnesium reactors. It would be appreciated by a person skilled in the art that the calcination of dolomite rocks is difficult to control because the inner part of the rocks calcine more slowly that the outer parts. Generally, when ground there is a wide distribution of the degree of calcination of the product. To achieve the specifications for the dolime, a large fraction of the particles from the outer parts of the rock have been overcooked and are highly sintered and unreactive. This overcooking leads to longer residence times, and that creates an energy penalty. The wide range of the reactivity of the dolime in the ferrosilicon process also leads to longer processing times, and inefficiencies. This disclosure optimizes the production process efficiency, as well as captures the CO.sub.2.

(16) Yet a further embodiment may use electrical power to heat a furnace to provide the energy for calcination. The energy for calcination may be produced, using, for example, resistive heating. In this embodiment, the furnace wiring is segmented to provide control of the heat transfer to the products such that the temperature profile of the solids passing down through the calciner is one in which, preferably, increases monotonically. Otherwise, the process is as described in the first embodiment.

(17) While particular embodiments of this disclosure have been described, it will be evident to those skilled in the art that the present disclosure may be embodied in other specific forms without departing from the essential characteristics thereof. The present embodiments and examples are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. It will further be understood that any reference herein to known prior art does not, unless the contrary indication appears, constitute an admission that such prior art is commonly known by those skilled in the art to which the invention relates.