AU8794198A

AU8794198A - Heating with steam

Info

Publication number: AU8794198A
Application number: AU87941/98A
Authority: AU
Inventors: David Stewart Conochie; Mark Howard Davies; Katherine Fiona Howison
Original assignee: EVERGREEN ENERGY Inc
Current assignee: EVERGREEN ENERGY Inc
Priority date: 1997-08-25
Filing date: 1998-08-25
Publication date: 1999-03-16
Anticipated expiration: 2018-08-25
Also published as: AU747552B2

Description

WO 99/IUU75 PCT/AU98/00688 -1 HEATING WITH STEAM The present invention relates to processing a 5 charge of a solid material to heat the solid material. The present invention relates particularly, although by no means exclusively, to processing a charge of a solid material which has low thermal conductivity under 10 conditions including high temperature and pressure. The present invention relates more particularly to: 15 (i) upgrading carbonaceous materials, typically coal, under conditions including high temperature and pressure to increase the BTU value of the carbonaceous materials by removing water from the 20 carbonaceous materials; and (ii) cooling the heated carbonaceous materials. US patent 5,290,523 to Koppelman discloses a 25 process for upgrading coal by the simultaneous application of temperature and pressure. Koppelman discloses thermal dewatering of coal by heating coal under conditions including elevated 30 temperature and pressure to cause physical changes in the coal that results in water being removed from the coal by a "squeeze" reaction. Koppelman also discloses maintaining the pressure 35 sufficiently high during the upgrading process so that the by-product water is produced mainly as a liquid rather than as steam.

WO 99/1UU78 PCT/AU98/00688 -2 Koppelman also discloses a range of different apparatus options for carrying out the upgrading process. In general terms, the options are based on the use of a 5 pressure vessel which includes an inverted conical inlet, a cylindrical body, a conical outlet, and an assembly of vertically or horizontally disposed heat exchange tubes positioned in the body. 10 In one proposal to use a Koppelman-type apparatus, the vertically disposed tubes and the outlet end are packed with coal, and nitrogen is injected to pre pressurise the tubes and the outlet end. The coal is heated by indirect heat exchange with oil that is supplied 15 as a heat transfer fluid to the cylindrical body externally of the tubes. Further heating of the coal is promoted by direct heat exchange between the coal and steam which acts as a working fluid within the packed bed. In addition, the steam pressurises the tubes and the outlet end to a 20 required pressure. The combination of elevated pressure and temperature conditions in the tubes and the outlet end evaporates some of the water from the coal and thereafter 25 condenses some of the water as a liquid. A portion of the steam generated following the addition of water also condenses as a liquid in colder regions of the tubes due to the elevated pressure. Steam which is not condensed, and which is in excess of the requirements for optimum 30 pressurisation of the packed bed, must be vented. In addition, non-condensable gases (eg CO, CO 2 ) are evolved and need to be vented. Periodically, liquid is drained from the outlet end. 35 Finally, after a prescribed residence time, the vessel is depressurised and the upgraded coal is discharged via the outlet end and subsequently cooled.

wO 99/1U078 PCT/AU98/00688 -3 The above described proposal to use a Koppelman type apparatus requires the use of oil as a heat transfer fluid at close to its operating temperature limit. This is 5 undesirable from environmental and occupational health viewpoints. Other high temperature liquids such as molten salt or molten metal may be used as alternatives but these also have limitations in use. 10 In another proposal to use a Koppelman-type apparatus, steam rather than oil is used as a heat transfer fluid in direct rather than indirect contact with coal. The disadvantages of this proposal include limited options to scale up to a commercial plant size and difficulties in 15 controlling heating rate. An object of the present invention is to provide an improved method and apparatus for upgrading coal by the simultaneous application of temperature and pressure which 20 does not rely on the use of oil as the heat transfer fluid. According to the present invention there is provided a method of heating a solid material in a process vessel, which method comprises: 25 (a) supplying a charge of the solid material to the vessel to form a packed bed; (b) supplying a fluid to the packed bed to 30 pressurise the contents of the vessel; (c) supplying steam to the vessel to heat the solid material in the packed bed by indirect heat exchange while maintaining 35 the contents of the vessel under pressure; and WO 99/100UU78 PCT/AU98/00688 -4 (d) controlling the operating conditions in step (c): (i) to transfer heat to the solid material 5 and allow water in the solid material to be removed as a liquid phase in a first "wet" stage of the method; and (ii) to transfer heat to the solid material 10 to boil at least a part of the remaining water from the solid material as a vapour phase in a second "dry" stage of the method. 15 The term "operating conditions" is understood to mean any conditions which have a bearing on the heating of the solid material and the removal of water from the solid material and includes, by way of example, operating conditions such as steam pressure, steam temperature and 20 steam flow rate which influence the temperature in the packed bed. It is preferred that step (d) comprises controlling the operating conditions so that a substantial 25 portion of the steam condenses during indirect heat exchange with the solid material in the packed bed in the wet phase of the method. It is preferred particularly that step (d) 30 comprises controlling the operating conditions so that at least 80% of the steam condenses during indirect heat exchange with the solid material in the packed bed in the wet phase of the method. 35 It is preferred that the wet stage of the method heats the solid material to a temperature of the order of 250 0

C.

WO 99/10078 PCT/AU98/00688 -5 It is preferred that the dry stage of the method includes: (i) a "dwell" part during which the remaining 5 water that is removed in the dry stage boils from the solid material; and (ii) a subsequent heating part during which the solid material is heated to a final 10 temperature. It is preferred that the final temperature of the solid material in the dry stage be on average in the range of 2700 to 420 0 C to ensure optimum upgrading of the solid 15 material. In order to achieve temperatures of at least 270 0 C in the dry stage, it is preferred that the method comprises supplying superheated steam during the dry stage 20 of the method. It is preferred particularly that step (d) comprises controlling the operating conditions so that the pressure of the superheated steam in the dry stage of the 25 method is greater than the pressure in the packed bed so as to promote boiling of water in the packed bed. Typically, step (d) comprises controlling the pressure of the steam in the wet stage relative to the 30 pressure in the packed bed so as to control the condensing temperature of the steam to be less than that of the boiling temperature of water in the packed bed. This step ensures operation which avoids boiling of water exuded from the solid material in the packed bed during the wet stage 35 of the method. It is preferred that the method comprises: woU 9Y/1UU75 PCT/AU98/00688 -6 (a) supplying superheated steam to a first process vessel to heat solid material in the packed bed in the first vessel by 5 indirect heat exchange during the dry stage of the method; (b) supplying steam discharged from the first process vessel to a second process vessel 10 to heat solid material in the packed bed in the second vessel by indirect heat exchange during the wet stage of the method. 15 The above described use of two (or more) process vessels with separate charges of solid material is particularly advantageous because it makes use of steam in a superheated state in the dry stage to heat the solid material in the packed bed to temperatures to boil water 20 from the solid material and to further heat the solid material to a final temperature and thereafter makes use of steam in the wet stage to heat solid material without boiling the water in the solid material. 25 It is preferred particularly that the method further comprises: (a) discharging heated solid material from the first vessel after completing the wet and 30 dry stages of the method and removing a required level of water from the solid material during these stages; (b) filling the first vessel with solid 35 material and pressurising the contents of the vessel; and WO 99/100I78 PCT/AU98/00688 -7 (c) changing the flow of steam so that the superheated steam flows first through the second vessel to heat the solid material in the packed bed by indirect heat 5 exchange in the dry stage of the method and the steam discharged from the second vessel flows through the first vessel and heats solid material in that vessel by indirect heat exchange in the wet stage of 10 the method. It is preferred more particularly that the method comprises repeating the above described sequence of steps of emptying and filling the vessels and changing the flow 15 of steam through the vessels. According to the present invention there is also provided an apparatus for heating a solid material which comprises: 20 (a) a process vessel for containing a packed bed of the solid material; and (b) a heat exchange circuit for supplying 25 steam to the process vessel to heat the solid material in the packed bed via indirect heat exchange, which heat exchange circuit comprises: 30 (i) a heat exchange assembly in the process vessel, which assembly comprises a passageway for steam and a plurality of heat exchange surfaces which, in use, extend into the packed bed; 35 (ii) a condenser for condensing steam discharged from the heat exchange WO 99/10U78 PCT/AU98/00688 -8 assembly; and (iii) a boiler for generating steam for the heat exchange assembly from the water 5 condensed in the condenser. It is preferred that the exchange circuit further comprises a means for storing steam to allow for variations in flow and pressure during normal operating conditions, 10 load/unload, start-up and shut-down. It is preferred that the apparatus comprises two or more process vessels for containing packed beds of the solid material. 15 With this arrangement, it is preferred that the heat exchange circuit comprises one of the heat exchange assemblies in each of the vessels and that the heat exchange assemblies be connected together so that steam can 20 flow in series or in parallel through the heat exchange assemblies. The present invention is described further by way of example with reference to the accompanying drawings, of 25 which: Figure 1 illustrates schematically one preferred embodiment of the method and apparatus of the present invention for heating a solid material; 30 Figure 2 illustrates schematically another preferred embodiment of the method and apparatus of the present invention for heating a solid material; and 35 Figure 3 illustrates schematically another preferred embodiment of the method and apparatus woU 9T1/UU7 PCT/AU98/00688 -9 of the present invention for heating a solid material. The following description is in the context of 5 heating coal to upgrade coal by removing water from the coal to increase the calorific value of the coal. The present invention is not limited to this application and extends to processing any suitable solid material. 10 The method and apparatus illustrated in Figure 1 is based on the use of a single pressure vessel 65 which is constructed to receive and retain a packed coal bed 67 under conditions of elevated temperature and pressure. 15 The process vessel may be any suitable type of pressure vessel, such as described in International applications PCT/AU98/00005 entitled "A Reactor", PCT/AU98/00142 entitled "Process Vessel and Method of Treating A Charge of Material", PCT/AU98/00204 entitled 20 "Liquid/Gas/Solid Separation, and PCT/AU98/00324 entitled "Enhanced Heat Transfer" in the name of the applicant. The disclosure in these International applications is incorporated herein by cross reference. 25 The apparatus further comprises a heat exchange circuit for supplying steam to the vessel 65 to heat the coal by indirect heat exchange. The heat exchange circuit comprises: 30 (i) an assembly of vertically disposed heat exchange plates, generally identified by the numeral 64, which define heat transfer surfaces and include passageways (not shown) for steam; 35 (ii) a condenser 62 connected to the outlet end of the heat exchange assembly 64 for WO 99/100U78 PCT/AU98/00688 - 10 condensing any steam that is not condensed; (iii) a boiler assembly 60 connected to the 5 condenser 62 for generating steam for the heat exchange assembly 64. The heat exchange circuit further comprises a steam accumulator 61 at the inlet end of the heat exchange 10 assembly 64 which stores steam and ensures controlled pressure in the passageways of the assembly 64 and a pressure control valve 63 at the outlet end of the heat exchange assembly 64. 15 The apparatus illustrated in Figure 1 further comprises a circuit, generally identified by the numeral 71, for circulating a working fluid through the packed coal bed 67 to enhance heat exchange between steam flowing through the heat exchange assembly 64 and coal in the 20 packed coal bed 67. The preferred working fluid is a gas that does not undergo a phase change in the operating conditions of the method. Gases that may be used as the working gas 25 include nitrogen, steam, SO 2 , C0 2 , hydrocarbons, noble gases, refrigerants, and mixtures thereof. The apparatus illustrated in Figure 1 further comprises an inlet 77 for introducing a gas into the vessel 30 65 to pressurise the vessel 65. In use of the apparatus illustrated in Figure 1 in accordance with a preferred embodiment of the method of the present invention: 35 (i) coal is supplied to the vessel 65 to form the packed coal bed 67; WO 99/10078 PCT/AU98/00688 - 11 (ii) the contents of the vessel 65 are pressurised with an externally supplied gas, internally generated steam, or both, 5 to a required pressure; (iii) steam is supplied to the heat exchange assembly 64 to heat coal in the packed coal bed 67. 10 The combined effect of pressure and temperature in the vessel 65 removes water from coal. The steam is supplied to the heat exchange 15 circuit 64 from the boiler assembly 60 at a temperature of at least 300 0 C. It is noted that the importance of avoiding devolatilisation of coal is one factor that determines the upper limit of the steam temperature. It is also noted that with other solid materials the maximum 20 steam temperature may be limited only by the boiler and not the solid materials. The accumulator 61 controls the supply of steam into the heat exchange assembly 64 to provide a reasonably 25 constant rate of condensation in the condenser 62. The pressure control valve 63 is used to control the pressure in the heat exchange assembly 64 and therefore control the condensation temperature. The settings required for the pressure control valve 63 are dependent on the heat 30 transfer on the coal bed side in the vessel 65. In the preferred embodiment of the method of the present invention, the operating conditions are controlled to remove water from the coal in two stages, with: 35 (i) water being "squeezed" from the coal and draining as a liquid phase to a lower WO 99/1UU78 PCT/AU98/00688 - 12 section of the vessel 65 in a first wet stage of the method; and (ii) a substantial part of the remaining water 5 in the coal being removed as a vapour phase in a second dry stage of the method. In the preferred embodiment of the method of the present invention the two-stage removal of water from coal 10 in the packed bed 67 is achieved advantageously using steam in the wet stage of the method and superheated steam in the dry stage of the method. The wet phase of the method can be operated 15 effectively with saturated steam and enables a substantial proportion (typically 80%) of the steam to be condensed. However, typically, steam will not heat coal in the packed bed to temperatures greater than 270 0 C that are required in the dry phase of the method to boil a substantial part of 20 the water remaining in the coal after the completion of the wet phase of the method. Typically, the dry phase requires final coal temperatures above the steam line and therefore saturated steam will not achieve these temperatures. 25 It is noted that the steam superheat temperature must be kept within the limits to which coal may be exposed without significant devolatilisation. This imposes limits on the balance of available heat in the wet and dry stage. In heating solid materials without the maximum temperature 30 constraint, there is more opportunity to optimise the use of energy in the steam. The applicant has found that it is preferable: 35 (i) to operate the dry stage of the method at steam pressure that is higher than the pressure in the packed coal bed 67 to WU 99/IUU78 PCT/AU98/00688 - 13 promote boiling of water in coal by condensation of supply side steam or to use superheated steam at any pressure; and 5 (ii) to operate the wet stage of the method at a steam pressure that is lower than that in the packed coal bed 67 to maintain the condensing temperature of the steam below the boiling temperature of water in the 10 packed coal bed 67. A feature of the above described control of the steam pressure to be higher than the bed side pressure in the dry stage of the method is that, when coupled with a 15 working fluid mass flow via circuit 71, there is a high rate of heat transfer not only to the coal particles but also to any water in the packed coal bed 67. This is a particularly important feature in the case wherein the bed is non-wetting and the heat transfer between solids and 20 liquids is low. The preferred embodiment of the present invention also comprises using reverse flow of working fluid in an asymmetrical configuration during the wet stage of the 25 method with longer pulses in a downward direction than in an upward direction to drive water in liquid phase downwardly towards the lower end of the vessel 65. Such asymmetrical working fluid flow can accelerate drainage of water from the packed coal bed 67. 30 The applicant has found that in a particular example the amount of heat required in the dry phase and the amount of heat required in the wet phase are roughly in proportion to that available from a single mass flow of 35 superheated steam, and this finding makes for a high efficiency of condensation of steam when using the invention. If higher amounts of steam are required in the wU 9/100UU/5 PCT/AU98/00688 - 14 dry phase, the efficiency of condensation is reduced unless it can be adequately restored with a higher degree of superheat. If lower amounts of steam are required in the dry phase then superheated steam is bypassed to the 5 saturation stage, and an efficiency approaching 100% should be achievable. The method and apparatus illustrated in Figure 2 is an extension of the arrangement illustrated in Figure 1 10 and is based on the use of two pressure vessels 65a, 65b. With reference to Figure 2, the apparatus comprises the same basic components illustrated in Figure 1, namely the process vessel 65a, 65b and the heat exchange 15 circuit. The apparatus further comprises two groups of flow control valves. A first group of valves LI, L3, R4, and R2 operate together and a second group of control 20 valves Rl, R3, L4 and L2 operate together, but in opposite phase to the first group of valves. Thus, when the first group of valves is open the second group of valves is closed. It can readily be appreciated that switching the state of each group of valves reverses the sequence of 25 steam flow through the vessels 65a and 65b. In use of the apparatus illustrated in Figure 2 in accordance with the preferred embodiment of the method of the present invention, after steady-state operation is 30 reached, the vessels 65a,65b are successively filled with coal, the vessels 65a, 65b are pressurised and the coal is heated in the preferred two-stage method by indirect heat exchange with steam, and the vessels 65a,65b are emptied after the completion of the second dry stage of the method. 35 Specifically, the flow of steam is successively changed through the vessels 65a,65b so that: WO 99/IUU78 PCT/AU98/00688 - 15 (i) firstly, superheated steam flows through the vessel 65a and heats coal in the dry stage of the method and the steam (which 5 is no longer superheated) discharged from the first vessel 65a flows through the second vessel 65b and heats coal in the wet stage of the method; and 10 (ii) secondly, superheated steam flows in the alternate path through the vessel 65b and heats coal in the dry stage of the method and steam discharged from the second vessel 65b flows through the vessel 65a 15 and heats coal in the wet stage of the method. The above described sequence of steps involves filling and emptying of each vessel 65a,65b and, as a 20 consequence, there will be dead times in the cycle of each vessel. In addition, in a preferred mode of operation, the first and second groups of valves are opened during a 25 changeover when one vessel 65a,65b is being emptied and filled and, thereafter, the required group of valves is progressively closed to avoid pressure waves in the system. The method and apparatus illustrated in Figure 3 30 is an alternative arrangement to that shown in Figure 2. With reference to Figure 3, the apparatus comprises 6 process vessels 65a, b, c, d, e, f (only one of which is shown in the figure) containing packed beds of 35 coal and a heat exchange circuit for supplying saturated steam and superheated steam to the vessels to heat the coal by indirect heat exchange in the wet and dry stages WO 99/10078 PCT/AU98/00688 - 16 described above in relation to Figures 1 and 2. There are a number of similarities and differences between the heat exchange circuit shown in 5 Figure 3 and that shown in Figures 1 and 2. One similarity is that the heat exchange circuit includes the assembly of vertically disposed heat exchange plates 64, the boiler 60, and the condenser 62. 10 One difference is that the heat exchange circuit includes a superheated steam header 91 and a saturated steam header 93 for storing superheated and saturated steam, respectively, upstream of the vessels. The headers 15 91, 93 are provided to allow for variations in flow and pressure in the heat exchange assemblies 64 in the vessels. A second difference is that, the heat exchange circuit includes a series of lines and valves to enable 20 separate supply of saturated steam via header 93 (line 81, valve V) and superheated steam via header 91 (line 83, valve V 2 ) to each of the vessels 65a, b, c, d, e, f to heat the coal under elevated pressure in the wet and dry stages as described above. 25 Furthermore, the heat exchange circuit includes: (i) a water/steam separator 95 at the outlet end of the heat exchange assembly 64 of each 30 vessel to separate steam and water discharged from the heat exchange assemblies 64; and (ii) lines 101 to transfer separated water to the 35 boiler 60 and lines 103 to transfer separated steam to the saturated steam header 93.

wU 919UUi/ PCT/AU98/00688 - 17 Many modifications may be made to the preferred embodiment described above without departing from the spirit and scope of the present invention. 5 For example it is within the scope of the present invention to combine the invention with energy recovery as described in the co-pending Australian provisional application of the applicant lodged on the same date as the 10 subject Australian provisional application. The disclosure in that other Australian provisional application is incorporated herein by cross reference.

Claims

1. A method of heating a solid material in a process vessel, which method comprises: 5 (a) supplying a charge of the solid material to the vessel to form a packed bed; (b) supplying a fluid to the packed bed to 10 pressurise the contents of the vessel; (c) supplying steam to the vessel to heat the solid material in the packed bed by indirect heat exchange while maintaining 15 the contents of the vessel under pressure; and (d) controlling the operating conditions in step (c): 20 (i) to transfer heat to the solid material and allow water in the solid material to be removed as a liquid phase in a first "wet" stage of the method; and 25 (ii) to transfer heat to the solid material to boil at least a part of the remaining water from the solid material as a vapour phase in a second "dry" 30 stage of the method.

2. The method defined in claim 1 wherein step (d) further comprises controlling the operating conditions so that a substantial portion of the steam condenses during 35 indirect heat exchange with the solid material in the packed bed in the wet phase of the method. wU 99/100iuu/5 PCT/AU98/00688 - 19

3. The method defined in claim 2 wherein step (d) further comprises controlling the operating conditions so that at least 80% of the steam condenses during indirect heat exchange with the solid material in the packed bed in 5 the wet phase of the method.

4. The method defined in any one of the preceding claims wherein the wet stage of the method heats the solid material to a temperature up to 250 0 C. 10

5. The method defined in any one of the preceding claims wherein the dry stage of the method includes: (i) a "dwell" part during which the remaining 15 water that is removed in the dry stage boils from the solid material; and (ii) a subsequent heating part during which the solid material is heated to a final 20 temperature.

6. The method defined in claim 5 wherein the final temperature of the solid material in the dry stage is on average in the range of 2700 to 420 0 C to ensure optimum 25 upgrading of the solid material.

7. The method defined in any one of the preceding claims comprises supplying superheated steam during the dry stage of the method. 30

8. The method defined in claim 7 wherein step (d) comprises controlling the operating conditions so that the pressure of the superheated steam in the dry stage of the method is greater than the pressure in the packed 35 bed so as to promote boiling of water in the packed bed.

9. The method defined in any one of the preceding WO 99/1UU78 PCT/AU98/00688 - 20 claims wherein step (d) comprises controlling the pressure of the steam in the wet stage relative to the pressure in the packed bed so as to control the condensing temperature of the steam to be less than that of the boiling 5 temperature of water in the packed bed.

10. The method defined in any one of the preceding claims comprises: 10 (a) supplying superheated steam to a first said process vessel to heat solid material in the packed bed in the first vessel by indirect heat exchange during the dry stage of the method; 15 (b) supplying steam discharged from the first said process vessel to a second process vessel to heat solid material in the packed bed in the second vessel by 20 indirect heat exchange during the wet stage of the method.

11. The method defined in claim 10 further comprises: 25 (a) discharging heated solid material from the first vessel after completing the wet and dry stages of the method and removing a required level of water from the solid material during these stages; 30 (b) filling the first vessel with solid material and pressurising the contents of the vessel; and 35 (c) changing the flow of steam so that the superheated steam flows first through the second vessel to heat the solid material wU 99/LUT PCT/AU98/00688 - 21 in the packed bed by indirect heat exchange in the dry stage of the method and the steam discharged from the second vessel flows through the first vessel and 5 heats solid material in that vessel by indirect heat exchange in the wet stage of the method.

12. The method defined in claim 11 comprises 10 repeating the sequence of steps of emptying and filling the vessels and changing the flow of steam through the vessels.

13. An apparatus for heating a solid material which comprises: 15 (a) a process vessel for containing a packed bed of the solid material; and (b) a heat exchange circuit for supplying 20 steam to the process vessel to heat the solid material in the packed bed via indirect heat exchange, which heat exchange circuit comprises: 25 (i) a heat exchange assembly in the process vessel, which assembly comprises a passageway for steam and a plurality of heat exchange surfaces which, in use, extend into the packed bed; 30 (ii) a condenser for condensing steam discharged from the heat exchange assembly; and 35 (iii) a boiler for generating steam for the heat exchange assembly from the water condensed in the condenser. WO 99/1UU78 PCT/AU98/00688 - 22

14. The apparatus defined in claim 12 wherein the exchange circuit further comprises a means for storing steam to allow for variations in flow and pressure during normal operating conditions, load/unload, start-up and 5 shut-down.

15. The apparatus defined in claim 13 or 14 further comprises two or more said process vessels for containing packed beds of the solid material. 10

16. The apparatus defined in claim 13 wherein the heat exchange circuit comprises one of the heat exchange assemblies in each of the vessels and the heat exchange assemblies be connected together so that steam can 15 flow in series or in parallel through the heat exchange assemblies.

17. A method of heating of solid material in a process vessel substantially as hereinbefore described with 20 reference to the accompanying drawings.

18. An apparatus for heating a solid material substantially as hereinbefore described with reference to the accompanying drawings. 25