APPARATUS FOR ENDOTHERMIC REACTIONS

Abstract

A carbonaceous feed pyrolysis apparatus is provided including two or more hot particle fluidised beds, one of which contains a combustion zone, and one or more positive displacement apparatus for the transfer of hot particles beds. Also provided is a bio-oil production process including two or more fluidised beds, a first combustion zone carried out in one or more combustion fluidised beds in which a particulate material is fluidised and heated, and a second pyrolysis zone carried out in one or more pyrolysis fluidised beds in which hot particles heated in the combustion zone are used for pyrolysis of bio-mass, the combustion zone being operated at or about atmospheric pressure at a temperature of from 400 C. to 1100 C., and the pyrolysis zone being operated at a pressure of from atmospheric to 100 Barg at a temperature of from 400 C. to 900 C.

Claims

1-20. (canceled)

30. An endothermic reaction process, comprising: providing an endothermic reaction apparatus, comprising: two or more fluidized bed zones comprising a first fluidized bed zone and a second fluidized bed zone; a second fluidized bed zone gas feed comprising a closed gas loop configured such that, in use, a portion of a gas produced in the second fluidized bed zone is recycled in the closed gas loop to the first fluidized bed zone, such that the recycled gas is used as a gaseous fuel for the first fluidized bed zone, either fully or in part; an apertured divider having one or more apertures therethrough connecting at least two of the fluidized bed zones; a mass transfer device for transferring particulate matter from at least one fluidized bed zone to an other fluidized bed zone; a gas loop purge configured such that, in use, a part of the recycled gas stream from the second fluidized bed zone is purged from the closed gas loop; and a flow rate regulator configured to, in use, regulate a flow rate to a predeterminable rate; combusting a carbonaceous material in a presence of oxygen in a hot first fluidized bed zone; carrying out one or more endothermic reactions in a second fluidized bed zone, wherein the second fluidized bed zone is separated from the first fluidized bed zone by an apertured divider; transferring a fluidized bed material from the hot first fluidized bed zone through one or more apertures of the apertured divider to the second fluidized bed zone; displacing fluidized bed particulate material below a fluidized bed of the second fluidized bed zone by means of a positive displacement mass transfer device; and recycling a portion of a gas produced in the second fluidized bed zone to the first fluidized bed zone in a closed gas loop, such that the recycled gas is used as a gaseous fuel for the first fluidized bed zone, either fully or in part, wherein a part of the recycled gas stream from the second fluidized bed zone is purged from the closed gas loop, wherein a flow rate is regulated to a predeterminable rate by a flow rate regulator.

21. The endothermic reaction process of claim 20, wherein a temperature in the second fluidized bed zone is regulated in relation to a rate at which the fluidized particulate material below the fluidized bed of the second fluidized bed zone is displaced.

22. The endothermic reaction process of claim 20, wherein a height of a fluidized bed of the hot first fluidized bed zone and a height of the fluidized bed of the second fluidized bed zone are self-regulated by material transfer between the two fluidized beds through the one or more apertures of the apertured divider.

23. The endothermic reaction process of claim 20, wherein fluidizing gas in the second fluidized bed zone is recirculated and solid and liquid products are removed as part of a recirculation loop, and wherein a portion of the recirculated fluidizing gas is introduced into the fluidized bed of the second fluidized bed zone through nozzles.

24. The endothermic reaction process of claim 23, wherein a net production of gas in the recirculation loop is removed as a purge.

25. The endothermic reaction process of claim 20, wherein excess gas is returned to the hot first fluidized bed zone where combustible gases are burned.

26. The endothermic reaction process of claim 20, wherein the process is a pyrolysis process comprising pyrolysis of a carbonaceous bio-mass, wherein a first combustion zone is carried out in one or more combustion fluidised beds in which a particulate material is fluidised and heated, and wherein a second pyrolysis zone is carried out in one or more pyrolysis fluidised beds in which the particulate matter fluidised and heated in the combustion zone is used for pyrolysis of the bio-mass, wherein the first combustion zone is operated at a temperature of from 400 C. to 1100 C., and wherein the second pyrolysis zone is operated at a temperature of from 400 C. to 900 C.

27. The endothermic reaction process of claim 26, wherein the second pyrolysis zone and the first combustion zone are at substantially a same pressure, so that levels of both beds are similar and so that there is a minimal flow of gas between the second pyrolysis zone and the first combustion zone, and wherein the endothermic reaction process is operated at a pressure of from atmospheric pressure to a pressure of 100 Barg.

28. The endothermic reaction process of claim 26, wherein the one or more combustion fluidised beds are in the hot first fluidised bed zone and the one or more pyrolysis fluidised beds are in the second fluidised bed zone, and wherein pyrolysis gas from the second pyrolysis zone is at least partially recycled to the first combustion zone as a source of fuel for the combustion used to heat the particulate matter.

29. The endothermic reaction process of claim 26, wherein the particulate matter fluidised and heated in the combustion zone is selected from the group consisting of sand particles, catalyst particles, and combination thereof, and wherein the particulate matter fluidised and heated in the combustion zone passes through the apertures of the apertured divider from the combustion zone into the pyrolysis zone.

30. The endothermic reaction process of claim 29, wherein the pyrolysis zone is operated at atmospheric pressure.

31. The endothermic reaction process of claim 29, wherein the catalyst is selected from the group consisting of a cracking catalyst and an acidic zeolite.

Description

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[0044] The invention will how be described, by way of non-limiting example only, with reference to the accompanying diagrammatic drawings. In the drawings,

[0045] FIG. 1 shows a flow diagram of an endothermic reaction apparatus; and

[0046] FIG. 2 shows a device for feeding heat-sensitive materials into a hot fluidised bed.

[0047] In the Figures, a basic endothermic reaction apparatus generally in accordance with the invention is shown. The apparatus consists of two fluidised beds 1 and 2 separated by a vertical divider 5. A positive displacement device such as an auger 3 moves the bed material from the reduction side to the combustion side of the device below the fluidisation zone.

[0048] The height of the two fluidised beds is equalised by movement of the bed material through a hole 4 in the vertical divider, from the high temperature side 1 (zone 1) to the low temperature side 2 (zone 2).

[0049] The bed material that moves through the hole 4 provides energy to drive reactions that may occur on the reduction side. Energy may also be provided to zone 2 by means of conductive and radiative heat transfer through the dividing wall 5. Energy is provided to zone 1 by means of an exothermic reaction, typically combustion of a fuel 13 using air 12.

[0050] The temperature in the reduction zone 2 may be controlled by the speed of the auger 3.

[0051] The fluidising gas in zone 2 is recirculated using blower 6. This gas may be cooled, and solid and liquid products may be removed (7 and 8 respectively) as part of the recirculation loop. The gas is introduced into zone 2 through nozzles 9. If there is a net production of gas in the recirculation loop, it may be removed as a purge 10. This may be a desired product of the reaction occurring in fluidised bed 2. The excess gas may be returned to zone 1 through line 11, and combustible gases will be burned in zone 1.

[0052] In previous inventions involving dual bed designs, the amount of gas recirculated through 11 or purged through 10 is controlled typically through the pressure in the freeboard above beds 1 and 2. In this invention it is proposed that the flow rate of the gas in streams 10 and 11 is set, and controlled at this set flow rate. This flow rate may be coupled to be proportional to the feed rate of reactant 14 to zone 2. If this set flow rate is less than the net rate of formation of gas in the recirculation loop 6, then there will be a net flow of gas from fluidised bed zone 2 to zone 1 through hole 4. Conversely, if the net flow in streams 10 and 11 is more than the net rate of formation of gas in the recirculation loop 6, then there will be a net flow of gas from fluidised bed zone 1 to zone 2 (and some nitrogen can be expected in lines 10 and 11 from the combustion air).

[0053] The total flow rate in streams 10 and 11 should be set according to a ratio proportional to the rate of feed 14. This ratio might change if conditions in zone 2 change (such as the temperature of zone 2).

[0054] The fluidized bed 2 may be arranged to surround the hotter fluidised bed 1. In this way, heat losses from the device as a whole are reduced, because the external walls where heat loss occurs are the walls of the colder fluidised bed, which makes thermal insulation easier. An instance of this is to have a vertical cylindrical fluidised bed 1, with the fluidised bed 2 forming an annulus around bed 1.

[0055] The nozzles 9 may be directed in such a way to induce a flow in the fluidised bed 2 in a circular motion around the axis of the annulus. This has the advantage that the bed is continually renewed at the location where reactants (stream 14) are introduced into the fluidised bed, thereby avoiding cold spots and prompting good mixing.

[0056] The separating wall 5 may be protected by a layer of heat and abrasion resistant material on either or both sides of the separating wall, particularly on the hot side (17) where metals are vulnerable to erosion due to the action of the fluidised bed 1 and the associated high temperatures.

[0057] Clinker that forms in the hot fluidised bed may be removed by an additional auger 18.

[0058] The outer wall of the annular colder zone 2 can be thermally insulated to prevent heat loss from the device as a whole.

[0059] As an example, the device may be used as a pyrolysis apparatus where the material to be pyrolysed is introduced directly into zone 2, char is removed at 7, the stream is cooled and bio-oil is removed at 8. The flow of gas in 11 is chosen to be approximately what can be expected from pyrolysis at the chosen conditions, and typically no gas exits through 10.

[0060] The gas provided by stream 11 is mixed with air before entering the combustion fluidised bed 1. Additional fuel (13) may be added to maintain the combustion fluidised bed (1) temperature (typically 850 C. to 950 C.). This fuel may be similar to the material added at 14, but will typically have a larger particle size.

[0061] The temperature of the pyrolysis fluidised bed 2 may be increased to increase the amount of gas produced, until the device as a whole is self-sufficient on feed 14, and requiring no fuel 13.

[0062] The temperature of the pyrolysis fluidised bed 2 may be increased further to increase the amount of gas produced, and additional gas will be released through 10. In this way, the device may be operated as a gasifier.

[0063] It is anticipated that the pyrolysis feed 14 may consist of traditional solid biomass, recycled plastics, car tires or coal, but may also be organic liquids such as glycerol of bio-oil, and this apparatus may be suitable to gasify or reform such feed material to a gas containing low nitrogen levels, using air rather than oxygen as the energy source. When operated as a gasifies, additional steam may be added to zone 2.

[0064] The selection of suitable flow rates in streams 10 and 11 allows the device to be operated easily at different pressures, including pyrolysis and gasification at high pressures such as 1-3 MPa. The annular pyrolysis device has a shape that is easily adapted to pressure operation.

[0065] The hot gases 15 can be used to generate steam, create shaft work through a turbine, or to heat treat char to give a higher quality product. Residual heat can be used to dry biomass before feeding it to the pyrolysis reactor through 14.

[0066] Zone 1 is normally operated as a combustion bed, but may alternatively be operated in a reducing atmosphere in which substantially all of the oxygen is reacted and carbon monoxide forms along with the carbon dioxide. This mode of operation is useful if the fluidised bed is composed mainly of char. Steam gasification can take place in zone 2 by replacing the blower 6 with a single or multi-stage steam eductor-jet pump. The hot gases 15 may then be burned in a secondary combustor/turbine 16 and the energy used as previously described.

[0067] Co-generated heat from stream 15 and heat emitted from the cooler represented by 8 can be used off-plant such as steam for process heat or hot water for house heating if the pyrolysis unit replaces a domestic furnace.

[0068] The bed material 1 and 2 can be a catalyst to produce targeted products in zone 2. Catalysts typically coke up at higher temperatures, and zone 1 is suitable for combusting such char and regenerating the catalyst. In this way, catalyst can be continually regenerated.

[0069] The bed material can be an oxygen carrier. The bed material can be chosen to react with oxygen in the feed material 14 in zone 2, and release such oxygen in zone 1 where it is heated to a higher temperature. An example of such a system is calcium oxide and calcium hydroxide or calcium carbonate.

[0070] The device that provides feed material to zone 2 (stream 14) may be injecting heat-sensitive material into a hot zone 2. This may be done using an auger that is partially filled with a liquid such as water or ethanol, promoting heat transfer from the part of the auger in contact with zone 2 to a part of the auger where the heat can be removed by cooling water or cooling air using cooling fins. The tube that houses the auger may be designed in a similar way as a heat tube to keep the auger cool. The auger screw may be hollow to allow the cooling fluid to reach the tip of the screw.

[0071] Alternatively, heat sensitive material may be introduced to zone 2 by a pneumatic injector. FIG. 2 shows how pneumatically conveyed solid material 19 is protected from heat transfer at the entrance to zone 2 by an annulus of cold air 20. Together the two gas streams provide the nozzle providing fluidisation gas to zone 2. The central tube should not extend into the bed, but father extend to slightly short of the bed by approximately one diameter of the outer tube.

[0072] A similar pneumatic feeder may be used for an annular shape of zone 2 by using a circular length of pipe for injecting the gas. The cool gas and solids are injected into the pipe tangentially, preferably with a narrowing of the pipe as it enters the circular pipe. This will act as an eductor to cause gas to circulate rapidly in the circular tube. Centrifugal force will cause the solid material to move along the outer wall of the circular pipe. Holes in the outer wall of the circular pipe act as fluidised bed nozzles, and the solid is injected into the fluidised bed through these nozzles. These nozzles may be directed tangentially to induce a circular motion to the bed within the annulus.

[0073] The circular pipe should be protected from the heat transfer provided by the fluidised bed particles. This can be achieved by providing a shield above the pipe with a small air gap between it and the circular pipe. Such a shield should be angled to allow the fluidised bed particles to slip off into the path of the fluidising gas.

[0074] Particles may clog the fluidised bed nozzles. This may be prevented by placing a ball in the circular pipe. The ball continually moves with the gas in the pipe, thereby preventing blockage of the fluidised bed jets. The diameter of the ball should typically be 0.9 to 0.5 times the inner diameter of the circular pipe.