PROCESS AND SYSTEM FOR THERMAL TREATMENT OF GRANULAR SOLIDS

Abstract

The invention relates to a process and the respective installation for thermal treatment of granular solids, in particular for producing aluminum oxide from aluminum hydroxide, wherein the solids are heated in at least one preheating stage and then reacted in a reactor at 700 to 1400 C. In at least one preheating stage, the average temperature gradient of the solids amounts to <15K/s and the dwell time of the solids amounts to 15 s.

Claims

1. A process for thermal treatment of granular solids, in particular for production of aluminum oxide from aluminum hydroxide, in which the solids are heated in at least one preheating stage and then are reacted in a reactor at 700 to 1400 C., characterized in that, the average temperature gradient of the solids amounts to <15 K/s and the dwell time of the solids amounts to 15 s in at least one preheating stage.

2. The process according to claim 1, characterized in that the solids are heated to 140 to 180 C. in a first preheating stage and/or heated to 200 to 400 C. in a preheating stage downstream from the first preheating stage and/or in the downstream preheating stage, the average temperature gradient of the solids amounts to <15 K/s and the dwell time of the solids amounts to >15 s.

3. The process according to claim 1 or 2, characterized in that the average temperature gradient of the solids in the first 10% of the dwell time is above the average temperature gradient over the entire dwell time.

4. The process according to claim 3, characterized in that, the average temperature gradient of the solids in the first 10% of the dwell time is more than twice as great as the average temperature gradient over the total dwell time.

5. The process according to any one of the preceding claims, characterized in that the solids are heated in countercurrent with the heating medium in at least two preheating stages connected after one another.

6. The process according to any one of the preceding claims, characterized in that at least one preheating stage is designed as a ring fluidized bed.

7. The process according to any one of the preceding claims, characterized in that the solids are first sent to a warming reactor in at least one preheating stage and then are sent to a residence time reactor.

8. The process according to claim 7, characterized in that the residence time reactor is operated in such a way that a stream of solids is removed through a drop pipe, wherein the stream of solids removed from the solids container is fluidized at the bottom of the downpipe by supplying a conveying gas and is transported to a higher level by means of a riser branching off from the downpipe, and the dwell time is varied by the stream of solids conveyed through the riser by means of the variable supply of the conveyor gas.

9. The process according to claim 7, characterized in that the warming device is a flash reactor or a plug-flow reactor.

10. The process according to claim 9, characterized in that the warming reactor is operated in countercurrent.

11. The process according to claim 7, characterized in that the temperature difference between the warming device and the residence time reactor is 30 K

12. An installation for calcining granular solids, in particular for carrying out a process according to any one of claims 1 to 11, having at least one preheating stage (10, 20) for preheating the solids and one reactor (30) for reacting the solids at 700 to 1400 C., characterized in that the at least one preheating stage (10, 20) is designed so that the average temperature gradient of the solids amounts to <15 K/s and the dwell time of the solids amounts to 15 s.

13. The installation according to claim 12, characterized in that at least one preheating stage (10, 20) has an annular fluidized-bed reactor or a combination of a warming reactor (40) and a residence time reactor (42).

Description

[0045] The drawings show schematically:

[0046] FIG. 1 shows schematically a system according to the invention,

[0047] FIG. 2 shows a preheating stage according to the invention,

[0048] FIG. 3 shows schematically a system according to the invention with a flash reactor and a residence time reactor,

[0049] FIG. 4 shows schematically a first system complex according to the invention,

[0050] FIG. 5 shows schematically a second system complex according to the invention, and

[0051] FIG. 6 shows schematically a third system complex according to the invention.

[0052] FIG. 1 shows schematically a system according to the invention for production of aluminum oxide. The starting material is aluminum oxide, which is supplied as a granular solid through a feed 11, for example, a screw conveyor, which sends it to the first preheating stage, where it is heated to 160 C. The heated solids are then sent through line 12 to a second preheating stage.

[0053] The aluminum hydroxide is heated further to a temperature of 400 C. in the second preheating stage 20. The preheating takes place here with a dwell time of 15 s and a temperature gradient of 13K/s, for example. To ensure this, the preheating stage 20 may also be designed in two stages, namely consisting of a preheating device and a residence time reactor.

[0054] Next, the partially dehydrated aluminum hydroxide is sent to a centrifugal separator 22 through a line 21. If the preheating stage 20 is designed in two steps, then it has proven advantageous in particular to position the residence time reactor downstream from the centrifugal separator 22 because in this way the residence time reactor can be designed with smaller dimensions.

[0055] Next, the heated solids are sent to a fluidized-bed reactor 30, which is supplied with gas through a line 31, so that aluminum hydroxide is calcined to aluminum oxide in a fluidized bed 32 at temperatures of 950 C.

[0056] It has proven advantageous to design the fluidized-bed reactor 30 as a circulating fluidized bed. To do so, a gas stream carrying the hot solids is supplied through a line 33 to a cyclone, in which the solids are separated from the gases. Some of the solids from the cyclone 34 are removed from the process through a line 35 and sent to a cooling unit (not shown), for example. The remaining solids are recirculated through a line 36 back into the fluidized bed 32 in the fluidized-bed reactor 30.

[0057] Instead of the fluidized-bed reactor 30, another calcination reactor may also be used, for example, a flash reactor.

[0058] The hot gas separated in the cyclone 34 can be removed through line 37 and used as the heating medium in a preheating stage. Using it in the second preheating stage 20 has turned out to be advantageous in particular because larger quantities of heat are necessary here than in the first preheating stage 10.

[0059] To increase the energy efficiency of the system, the hot gas may also be sent from the cyclone 22 through a line 24 to the first preheating stage 10 and/or heat generated in the cooling of the product (not shown) may be utilized in at least one of the preheating stages 10, 20.

[0060] One problem with recycling the heated gases to the preheating stage designed according to the invention is that the temperatures can fluctuate greatly there. For example, temperature fluctuations between 970 C. and 1100 C. must be assumed in production of aluminum. Temperature regulation is thus absolutely essential.

[0061] The preheating stage 20 according to the invention shown in FIG. 2 is designed as a ring fluidized-bed reactor.

[0062] The granular solids are introduced into the preheating stage 20 through a feed 210. The solids enter a fluidized bed 202 there.

[0063] The solids are brought to the temperature required for the reaction in this fluidized bed 202 by means of the gas introduced through a line 203 into a central tube 204. Preheated solids repeatedly enter the ring-shaped fluidized bed 202 into a fluidized mixing chamber 205 formed above it, where they are partially removed from the preheating stage 20 through an outlet 206. The remaining amount of solids drop back into the fluidized bed 202.

[0064] The preheating stage 20 is preferably designed with a double jacket 208 to prevent heat losses.

[0065] The central tube 204 has the thinnest possible wall thickness of 100 or 150 mm to permit the best possible heat transfer.

[0066] If there is a shortage of hydrate, the solids can also be acted upon by water from a nozzle 207 in the fluidized mixing chamber 205.

[0067] An endothermic reaction normally takes place in the fluidized mixing chamber 205: aluminum trihydroxide to aluminum monohydroxide. This causes a strong cooling of the exhaust gas from the reactor 30. If the hydrate mass stream 201 entering the reactor is then reduced, less reaction heat is consumed accordingly, the exhaust gas from the reactor 30 is not cooled sufficiently and the downstream equipment and pipelines are threatened with damage. Therefore, water is sprayed in through the nozzle 207 and completely evaporates at the temperature of the second preheating stage. Then the heat of evaporation of the water entirely or partially replaces the reduced heat consumption for the chemical reaction.

[0068] The cover of the preheating stage 20 is connected to the reactor by welded flange connections 209, so that the reactor can be opened relatively easily and the central tube 203 can be replaced.

[0069] Finally, FIG. 3 corresponds essentially to FIG. 1 and also shows the diagram of a calcination installation according to the invention. The individual preheating stage 20 designed as a ring fluidized bed is replaced here by a heating reactor 40 and the downstream residence time reactor 42.

[0070] The material to be preheated is conveyed through line 12 to the heating reactor 40. This heating reactor 40 can be operated with hot gases from the cyclone 34 or by some other process. There is preferably rapid heating of the solids here, i.e., with a temperature gradient in the first 10% of the total dwell time which is above the temperature gradient over the total dwell time.

[0071] The temperature gradient obtained as the quotient of the temperature difference to the total dwell time is regarded as the average temperature gradient over the total dwell time. The temperature difference is the difference between the inlet temperature of the solids on entrance into the warming reactor 40 and the outlet temperature of the solids on discharge of the solids from the residence time reactor 42. The total dwell time corresponds to the dwell time between the entrance and outlet of the solids out of the residence time reactor 42.

[0072] The material heated in this way, preferably already at a temperature at most 20 C., preferably only 10 C. from the final preheating temperature to be reached, is removed from the warming reactor 40, which is preferably designed as a flash reactor, through line 41 and sent to the residence time reactor 42. The residence time reactor 42 is especially advantageously designed, so that it serves as the solids transport device at the same time, which is implemented, for example, by an immersion pot.

[0073] Then the preheated solids go through line 21 into the downstream system parts known from FIG. 1.

[0074] According to the flow chart of the process according to the invention shown in FIG. 4, moist aluminum hydroxide (Al(OH).sub.3) is charged through line 101 to a hydrate filter 100, where it is cleaned with wash water.

[0075] The hydrate filter is preferably equipped with a vapor hood, so that the hydrate is already partially dried during filtration. The filtrate is sent through line 102, preferably by a conveyor screw (not shown) to a first preheating stage 106, where it is preheated to a temperature between 100 and 200 C.

[0076] Then the hydrate is sent through a line 107, 107 into a Venturi nozzle 110, out of which the exhaust gases are sent through line 112 into an electrostatic gas purification (ESP) 108. From there, the exhaust gases are sent at a temperature of 110 to 170 C., preferably 120 to 140 C., through the line 109 into a chimney (not shown). The solids emerging from the electrostatic gas purification 108 then pass through a line 111 directly to the product of calcination.

[0077] The solids are conveyed out of the solid separator 110 through line 119 and into a second preheating stage 128. In this stage, the solids are heated to a temperature of 150 to 300 C. and sent to a separating cyclone 115 through line 113. The exhaust gas stream of the separating cyclone 115 is sent through line 114 to the heat exchanger 106, to heat the hydrate and convey it to the electrostatic filter 118.

[0078] The solids from the separation cyclone 115 are sent through lines 116 and 118 to a fluidized-bed reactor 120, where the solids are calcined at temperatures of 850 to 1100 C., in particular approximately 950 C., and dehydrated to aluminum oxide (Al.sub.2O.sub.3).

[0079] The feed of the fuel required for the calcination takes place through a line 151, which is arranged at a slight height above the grating of the fluidized-bed reactor 120.

[0080] The gas streams containing oxygen required for combustion are sent through a feed line 154 as a fluidizing gas and through line 132 as secondary air. As a result of the gas feed, a relatively high suspension density is established in the lower area of the reactor, between the grating and the secondary gas feed 132, while a comparatively low suspension density prevails above the secondary gas feed 132. Without further heating, the primary air is fed at a temperature of approximately 80 C. into the fluidized-bed reactor 120 after the usual compression, where the temperature of the secondary air is approximately 550 C.

[0081] The gas-solids suspension enters the recirculation cyclone 122 of the circulating fluidized bed through line 123, where there is a renewed separation of solids from gas. The solids leaving the recirculation cyclone 122 through line 124 at a temperature of approximately 950 C. are fed into a mixing container 125. The solids separated in the electrostatic gas purification 108 and the solids from lines 116, 117 are also mixed in the mixing container 125 through line 111. The mixing container 125 preferably has a fluidized bed to achieve a complete and thorough mixing. Long dwell times of 30 minutes or more are also advantageous here.

[0082] The resulting product is supplied to a suspension cooler 130 through a line 26, 131 from mixing container 125. The exhaust gas from the suspension cooler 130 goes through line 132 as the secondary air into the fluidized-bed reactor 120. The solids from the suspension cooler 130 are introduced into the suspension cooler 137 through line 133, 139. The exhaust gas is returned to the cooler 130 through line 131, 131, while the solids are removed through line 138.

[0083] The aluminum oxide from line 138 is subjected to a final cooling in a fluidized-bed cooler having a plurality of cooling chambers, which are charged with fluidizing air through a line 150. The aluminum oxide enters the first chamber at a temperature of approximately 300 C. and heats a liquid heating medium, in particular water, to a temperature of 140 to 195 C. In a second heating chamber, the aluminum oxide is also cooled with water, which is supplied through line 155 and removed again through line 157. Gas is preferably used for cooling in the one or two following chambers of the fluidized bed cooling 140.

[0084] FIG. 5 shows a system of a similar design for calcination, but differentiated in several regards from the process illustrated in FIG. 4.

[0085] First, a line 103, which opens into a hydrate dryer 104, branches off from the line 102. The hydrate is heated to a temperature of 100 to 110 C. in the hydrate dryer by indirect heat exchange with a liquid heating medium, in particular water, and then is dried almost completely starting from a moisture content of approximately 6% by weight. Next, it is sent to the preheating stage 106 through a line 105 in a known way.

[0086] The water for heating the hydrate comes from the fluidized bed cooling 140 of the product and is supplied through line 141 and then removed again through line 142, thus creating a closed circuit between the hydrate dryer 104 and the first chamber of the fluidized bed cooling 140.

[0087] In addition, a process according to FIG. 5 has another preheating stage, so that this shows the preheating stages 106, 114 and 115. The material is therefore supplied first through the line 111 to the second preheating stage 114, from which it goes through the line 118 to the centrifugal sections 110. The exhaust gases from the centrifugal section 110 are supplied in a known way through line 112 only to the first preheating stage 106 and thus serve as the heating medium. The solids are sent through line 119 to a second preheating stage 128 and from there through line 113 into a centrifugal segment 115.

[0088] Finally, FIG. 5 shows another suspension heat exchanger, so that there are a total of three suspension heat exchangers 130, 134 and 137 downstream from reactor 120.

[0089] FIG. 6 shows a greatly simplified process for producing Al.sub.2O.sub.3, where the material is charged through line 301 and hydrate filter 300. The reactant is removed through line 302 and sent to the first preheating stage 304. The preheated material is sent to the centrifugal separator 310 through the line 305.

[0090] The exhaust gas is sent through line 311 to a second centrifugal separator 312. The solids are discharged into line 317 through lines 314 and 315.

[0091] The collected exhaust gas is sent through line 313 to an electrostatic gas purification 318, from which purified exhaust gases escape through line 319, while the solids are discharged through line 336.

[0092] The solids reaching the second preheating stage 320 through 317 are further heated there with an appropriate dwell time in the manner according to the invention and then sent through line 321 to a second centrifugal separator 322, which carries the solids through line 324 into the fluidized-bed reactor 330 and its respective centrifugal separator 331. The solids are separated by additional feed of fluidizing gas through line 335 and removal of the solids through line 338.

[0093] The exhaust gas from the centrifugal separator 322 is sent as the heating medium through line 323 to the first preheating stage 304.

[0094] Fuel is supplied to the reactor 330 through line 333 for creating the desired temperature. Fluidizing air enters the reactor through line 334. Additional gas is conveyed into the reactor through line 335, also conveying the solids out of line 336.

[0095] In addition, secondary air from line 341 goes through cyclone 340 and line 342 into the reactor 330.

EXAMPLE 1

[0096] In a system equipped according to the diagram in FIG. 6, 50,000 kg/h aluminum hydrate with a moisture content of 7 wt-% water is fed into the system at ambient temperature. In the first preheating stage 304, the hydrate is brought to a temperature of 170 C. Next it is heated to 370 C. in a second preheating stage 320 before being calcined at 1000 C. in the reactor 332. The following particle fractions with particles <45 m in size are obtained in the second preheating stage, depending on the course of heating, from 170 C. to 370 C. for a given time:

TABLE-US-00001 TABLE 1 Particle fraction Test Dwell time Heating ramp (n) <45 m V1 10 s 20 K/s 39% by wt. V2 30 min 0.111 K/s 33% by wt. V3 60 min 0.056 K/s 29% by wt. V4 90 min 0.037 K/s 29% by wt. V5 60 min 1 min at 3 K/s + 29% by wt. 59 min at 0.0056 K/s

[0097] Test V1 shows traditional heating: In comparison with that, tests V2, V3 and V4 show that the particle fraction can be greatly reduced by definitely heating more slowly. Test V5 shows that even a first rapid heating with a first ramp and subsequent stabilization by a second heating ramp, which is much slower, still yield the effect according to the invention, which can be understood as an interaction of the heating rate and the dwell time.

EXAMPLE 2

[0098] In a system equipped according to the diagram in FIG. 1, 250,000 kg/h aluminum hydrate with a moisture content of 7 wt-% water is fed into the system at ambient temperature. In the first preheating stage 10, the hydrate is brought to a temperature of 165 C. Next it is heated to 330 C. in a second preheating stage 20 before being calcined at 1000 C. in the reactor 30.

[0099] In a first run, particles' residence time in the second preheating stage 20 is 2-5 s. Due to a temperature rising of 165 C. (=330 C.-165 C.) the heating rate is between 33 and 82.5 K/s and, therefore, >15 K/s. As a result, about 5 wt-% particles with a diameter 10 m are obtained.

[0100] In comparison, a system according to FIG. 3 is used. Again, 250,000 kg/h aluminum hydrate with a moisture content of 7 wt-% water is fed into the system at ambient temperature. In the first preheating stage 10, the hydrate is brought to a temperature of 165 C. In a second preheating stage 40 it is heated to 330 C. with and average residence time between 2 and 5 s (like above) and afterwards fed into a residence time reactor 42 (holding reactor) before being calcined at 1000 C. in the reactor 30. In the residence reactor, the preheated material is stored at a temperature between 280 and 350 C., preferably at the same temperature as the target temperature of the second preheating stage 42 (here: 330 C.) in such that way, that the sum of the average residence times in the second preheating stage 40 and the afterwards residence reactor is 15 s, which leads to an average temperature gradient of 11 K/s. In comparison to a system described above, the amount of particles with a diameter 10 m is reduced from 5 to 3 wt-%.

[0101] By further increasing the average residence time in the residence time reactor to an overall average residence time of 180 s, particle breakage can be reduced further due to the healing of defects in the crystal lattice by keeping the particles and the temperature of the second preheating stage. The average temperature gradient for such a system would be 0.92 K/s. As a result, only 1-2 wt-% of the particles show a diameter 10 m for a process in FIG. 3 using the given values.

[0102] As a result, it is possible to reduce particles breakage significantly by extending residence times and, therefore, also average temperature gradient over the preheating itself and the residence reactor afterwards. So it is possible to increase the turnover of plants for calcining alumina.

LIST OF REFERENCE NUMERALS

[0103] 10 preheating stage [0104] 11,12 line [0105] 20 preheating stage [0106] 21 line [0107] 22 cyclone [0108] 23,24 line [0109] 30 reactor [0110] 31 line [0111] 32 fluidized bed [0112] 33 line [0113] 34 cyclone [0114] 35-37 line [0115] 40 warming reactor [0116] 41 line [0117] 42 residence time reactor [0118] 100 hydrate filter [0119] 101-103 line [0120] 104 hydrate dryer [0121] 105 line [0122] 106 preheating stage [0123] 108 electrostatic gas purification [0124] 109 line [0125] 110 solids separator [0126] 111-113 line [0127] 114 preheating stage [0128] 115 solids separator [0129] 116-118 line [0130] 120 fluidized-bed reactor [0131] 121 line [0132] 122 solids separator [0133] 123, 124 line [0134] 125 mixing container [0135] 126 line [0136] 130 suspension cooler [0137] 131-133 line [0138] 134 suspension cooler [0139] 135, 136 line [0140] 137 suspension cooler [0141] 138, 139 line [0142] 140 fluidized bed cooler [0143] 141-143 line [0144] 151-158 line [0145] 201 feed [0146] 202 annular fluidized bed [0147] 203 line [0148] 204 central tube [0149] 205 fluidized mixing chamber [0150] 206 outlet [0151] 207 nozzle [0152] 208 double jacket [0153] 209 welded flange connections [0154] 300 hydrate filter [0155] 301, 302 line [0156] 304 preheating stage [0157] 305 line [0158] 310 centrifugal separator [0159] 311 line [0160] 312 centrifugal separator [0161] 313-317 line [0162] 318 electrostatic gas purification [0163] 319 line [0164] 320 preheating stage [0165] 321 line [0166] 322 centrifugal separator [0167] 324 line [0168] 330 fluidized-bed reactor [0169] 331 recirculation cyclone [0170] 333-338 line [0171] 340 centrifugal separator [0172] 341, 342 line