This invention relates to a plant and a process for treating lignocellulosic biomass to produce organic chemicals, particularly but not exclusively to produce sugars; and particularly but not exclusively to a plant and process for achieving hydrolysis of cellulose.
As explained in EP 2483331B (Nova Pangaea), there are environmental problems that arise from the use of fossil fuels, so that use of biomass as a source for fuel and organic chemicals would be advantageous. Woody or lignocellulosic biomass is largely composed of hemicellulose, cellulose and lignin. Cellulose is principally comprised of C6 sugars while hemicellulose comprises both C5 and C6 sugars. Lignin is a complex polymer which gives physical strength to the biomass but which is tightly bound to the other components. Consequently it is not straightforward to remove the sugars from the remainder of the biomass. EP 2483 331B teaches a method of fractionating lignocellulosic biomass by a sequence of steps. Biomass may be fed into a hemicellulose hydrolysis reactor to hydrolyse hemicellulose, so a liquid component includes the products of hemicellulose hydrolysis for example in water, and so that the remaining solid component includes cellulose and lignin. The remaining solid component is then fed to a cellulose hydrolysis reactor which may apply steam at a temperature of between about 400° and 550° C., so as to hydrolyse cellulose and vaporise the resulting sugars; and then condensing the resulting vapours. The remaining solids may be in the form of a lignin char.
EP 2483 331B envisages the potential use of a wide range of different types of biomass, including wood, corn, straw, grass and other cellulose wastes; and indicates that the material may be pretreated for example by drying, and by comminution to create chips or flakes, indicating a preferred size of flakes being of thickness between 1 mm and 3 mm In addition, where appropriate, the material may be pretreated to remove volatile components such as natural oils. The hemicellulose hydrolysis reactor may treat the material using steam at a temperature for example between 170° and 250° C. and at an elevated pressure for example between 10 bar(a) and 35 bar(a). These conditions are described in EP 2483 331B as being sufficient to hydrolyse hemicellulose while minimising degradation of the biomass material. The sugars produced by hemicellulose hydrolysis will dissolve in water, and may be removed from the biomass using additional water and a counter current water flow; use of a screw press to remove liquid is also mentioned. The resulting solid material consists primarily of cellulose and lignin.
EP 2483 331B goes on to say that the solid material may be subjected to treatment such as drying and a further size reduction, before being subjected to a process to bring about cellulose hydrolysis. This may be achieved using flash thermolysis using superheated steam, which may for example be at a temperature between 350° and 550° C., and for example at a pressure between 1 bar(a) and 2 bar(a), such that the bond between lignin and cellulose is broken and the cellulose is hydrolysed into C6 sugars. The vaporised sugars and any other volatile compounds may then be separated from solid matter, and the vapours condensed to form an aqueous solution.
Although EP 2483331B describes a range of different ways of performing these steps, research has shown that there are a number of problems that must be resolved. In particular it has been found that use of superheated steam at a temperature of at least 500° C., for example 550° C., is advantageous in achieving hydrolysis or thermolysis of cellulose, but that there are a number of technical problems in ensuring that this operates consistently, at such a high temperature. For consistent performance it is necessary to ensure a consistent ratio between the mass of steam and the mass of particulate material (which ratio may be called the modulus), so that it is important to ensure that the particulate material is fed into the flow of steam at a consistent rate. For example if the flow of particulate material is irregular or comes in pulses, while the steam flow is kept constant, this results in uncontrolled reaction conditions, and risks loss of entrainment. Furthermore it has been found that the particles tend to become sticky when they are an elevated temperature, possibly due to melting of lignin, so it is highly desirable to keep the particles separated from one another as they pass through the reactor, to avoid agglomeration with the formation of large particles, and a build-up of deposits on the walls of the reactor. To a large extent these problems of stickiness can be resolved as long as the individual particles remain entrained in the flow of steam, so for this reason also a consistent flow rate of biomass into the reactor is highly advantageous.
The reaction between the high-temperature steam and the cellulose, which may be referred to as hydrolysis or thermolysis, is typically completed in less than 1 second, and the particles are then no longer sticky, consisting primarily of charred lignin. At this stage the sugars produced by the hydrolysis of cellulose are in vapour form. Downstream of the reactor it is therefore necessary to separate the remaining particles from the steam and vapours, and to condense the steam and vapours. Experiments have shown that there is a risk of the formation of blockages, which lead to a build-up of pressure and a backflow of steam; since, as explained above, consistent steam flow is highly desirable, it is important to ensure that the risk of formation of blockages is minimised.
According to a first aspect of the present invention there is provided a plant for performing thermolysis of cellulose, comprising a thermolysis reactor, the thermolysis reactor comprising a reactor duct having a longitudinal axis, and an eductor at one end of the reactor duct, the eductor comprising an entry chamber and a venturi-shaped exit channel, a nozzle, a sloping deflector plate above the nozzle, and an inlet port through which particulate material may be fed onto the deflector plate and into the entry chamber, the nozzle and the venturi-shaped exit channel both being aligned with the longitudinal axis of the reactor duct, and means for providing superheated steam at a temperature above 450° C. and for supplying the superheated steam to flow through the nozzle.
It will be appreciated that the chemical processes that take place when performing the operation referred to here as thermolysis may alternatively be referred to as hydrolysis, pyrolysis, depolymerisation or degradation; the overall result is that cellulose is separated from lignin and is broken down into smaller compounds. In this document the process of treating the material with high temperature steam to create smaller compounds from the cellulose is referred to as cellulose thermolysis, whereas this process was referred to as hydrolysis in EP 2483331.
During operation the superheated steam may be at a temperature of for example 550° C., and may be fed to the nozzle at a pressure of for example less than 1.5 bar(a). The nozzle is therefore at the same temperature. The deflector plate ensures that the particles of the particulate material do not come into contact with the nozzle, but rather are entrained by the flow of steam from the nozzle.
For example a source of high pressure steam may be available at a pressure of 10 bar(a). In such a case the steam supply to the thermolysis reactor may comprise a pressure-reducing valve to throttle the pressure down to about 1.5 bar(a). The flow rate of the steam through the nozzle is primarily determined by the steam pressure and the restriction imposed by the nozzle, but in addition there may also be a flowmeter, operating in conjunction with an up-stream flow-control valve, to monitor and tightly control the flow rate of the steam. The plant may also include a superheater to ensure the steam reaches the eductor nozzle at the desired temperature, which may be 550° C., and may be at a pressure of 1.3 bar(a); the superheater should be close to the thermolysis reactor, with minimal bends in the steam flow path, and with thermal insulation to minimise heat loss. The superheater may for example be electrically heated.
In one embodiment the particulate material is fed into the inlet port from a hopper using a twin screw conveyor. The twin screw conveyor provides a pressure barrier between the hopper and the reactor, so as to inhibit any backflow of steam, and to prevent material being uncontrollably sucked into the reactor. It is advantageous if the particulate material is of substantially uniform particle size.
In operation of the plant a steam velocity through the reactor of above 8 m/s may be used, more preferably above 10 m/s for example 12 m/s. Furthermore the modulus, that is to say the ratio between the mass flow of steam compared to the mass flow of particulate matter, is at least 3, for example 3.5, 4.0, 4.5, or 5.0. The steam cools as it heats the particulate material, so the resultant temperature of the particles may be in the range 370° C. to 450° C. The length of the reactor duct should be such as to ensure that the particles reach the end of the reactor duct in less than 1 s. For example the reactor duct may be of length 6.0 m if the steam velocity is 12 m/s, so that the particles take about 0.5 s to pass through the reactor duct.
The downstream end of the reactor may incorporate a screw mechanism, the screw flights having a diameter less than 70% of the reactor duct, for example 60% or 50%, to remove any particles of char that deposit on the wall of the reactor duct. Rotation of the screw transfers any particulate material to a position along the reactor duct wall where a char outlet port may be provided. By way of example the flights may be of consistent shape along the length screw, so as to convey the particulate material to one end of the screw, or alternatively the flights along part of the screw may be left-handed while those along the remainder of the screw are right-handed, so as to convey the particulate material to an intermediate position along the length of the screw.
The plant for performing thermolysis of cellulose may also incorporate a cyclone downstream of the reactor duct to remove and collect entrained particulate material. In this case a feed duct must convey the superheated steam and entrained particles from the downstream end of the reactor duct to the cyclone, feeding the flowing material through an entry port into the cyclone to ensure cyclonic flow. This entry port may for example be of a rectangular shape. Preferably there are no abrupt reductions in the cross-sectional area through which the superheated steam and entrained particles flow between the reactor duct and the input port for the cyclone, and no abrupt changes in flow direction.
The plant for performing thermolysis of cellulose may also incorporate a condenser, to condense the steam and the sugars and other vapours produced by the thermolysis. This may use a heat exchanger in which a coolant flows in heat exchanger channels that are in thermal contact through heat-conducting walls with flow channels for the steam and vapours. Alternatively it may use direct contact with a cooling liquid. By way of example there may be two successive cooling devices, the first acting as a desuperheater, for example by spraying a liquid so as to decrease the vapour temperature to just above the saturation point. The second may be arranged to achieve full or at least partial condensation of all the steam and vapours present, and may for example feed a coolant liquid onto trays so that coolant overflowing from the trays cascades down in counter current to the hot vapours.
The plant may also include a fan downstream of the condenser, to maintain flow of any gases or vapours that are not condensed by the condenser, and to generate the required underpressure in the reactor. For example there may be some air entrained with the particulate material that is fed into the reactor.
The present invention, in another aspect, provides a process for performing thermolysis of cellulose, using the plant of the first aspect, described above. This process may also have the optional features described above in relation to the plant.
The particulate material which is fed to the reactor must contain cellulose. Many types of biomass contain cellulose, but typically also contain other compounds, particularly hemicellulose and lignin. Typically the particulate material is produced by pre-treating biomass to remove the hemicellulose. As described in EP 2483331B this may be achieved by hemicellulose hydrolysis; a hemicellulose hydrolysis reactor may treat the material using steam at a temperature for example between 170° and 250° C. and at an elevated pressure for example between 10 bar(a) and 35 bar(a). After washing and drying, the resulting solid material consists primarily of cellulose and lignin. An acid such as phosphoric or sulphuric acid may be added to the biomass before it is subjected to the hemicellulose hydrolysis. It has been found that the hemicellulose hydrolysis step is more effective if an acid is present, and can be carried out at a somewhat lower temperature, for example no higher than 180° C. To some extent the hemicellulose hydrolysis reaction may be autocatalytic, because of formation of organic acids such as acetic acid. Nevertheless the addition of an acid prior to starting the hydrolysis is beneficial in ensuring satisfactory hydrolysis at a lower temperature than would otherwise be required.
Hence in a further aspect the present invention provides a plant to process particulate biomass, comprising a hemicellulose hydrolysis reactor, means to feed the particulate biomass into the hemicellulose hydrolysis reactor, means to separate water and water-soluble compounds from a resulting particulate material, and means to feed the resulting particulate material to the cellulose thermolysis plant described above.
In a further aspect the present invention provides a process for processing particulate biomass, the process comprising subjecting the biomass to hemicellulose hydrolysis in a hemicellulose hydrolysis reactor; separating water and water-soluble compounds from a resulting particulate material, and then subjecting the resulting particulate material to the cellulose thermolysis process descried above.
The separating of the particulate material from the water and water-soluble compounds may involve a filter or press, and may involving a rinsing or washing step. The particulate material may then be dried, to evaporate excess moisture, before being supplied to the cellulose thermolysis plant; the dried particulate material may also be subjected to a size reduction, for example with a mill, as particles of a more consistent size will be fed more consistently into the reactor, and small particles will heat through more quickly in the superheated steam.
The aqueous mixture formed as a result of the washing step contains the soluble products of hemicellulose hydrolysis, which are predominantly C5 sugars (such as xylose), with some C6 sugars (such as glucose and mannose). The products of cellulose thermolysis may be referred to as C6 sugars, but in practice consist of a mixture which may for example contain glucose, levoglucosan, levoglucosenone, oligomeric anhydrosugars, sugar oligomers and sugars chemically bound to phenol derivatives. The proportions may depend on the exact chemical composition of the solid component that is being treated, and the type of acid present. The cellulose thermolysis principally produces the volatile compound anhydroglucose, which may be referred to as levoglucosan.
The invention will now be further and more particularly described, by way of example only, and with reference to the accompanying drawings in which:
Referring to
After performing any such pre-treatment, the biomass is impregnated 12 with a strong acid, for example with dilute sulphuric acid (i.e. about 1 mole/L) typically at a rate of between 1-2 wt % of the dry biomass, before being introduced by a screw conveyor into a reactor 14 in which the biomass is contacted with steam/water at a temperature of between 150° and 180° C. and a pressure of between 6 bar and 10 bar, for example at 165° C. and a pressure of 6.5 bar (gauge); there is little air present. This may be a tube reactor along which the biomass travels along with the high-pressure steam/water. Under these reaction conditions the hemicellulose breaks down mainly to form C5 sugars, with also some C6 sugars, and organic acids, depending on the inherent composition of the biomass being processed.
At the operating pressure of 6.5 bar, the water at 165° C. is liquid as long as the pressure is maintained. As the material leaves the reactor 14 it may be cooled by depressurisation, exploding the biomass. A proportion of the water evaporates, typically about 10%, cooling the remaining biomass to below 100° C. For example the mixture of biomass and hot water may be released in slugs from the reactor. As mentioned above, it is necessary to remove the liquid phase from the treated biomass before it can be subjected to the second reaction step, both to remove sugars and to remove alkali material and any inorganic acid. Although some of the liquid may be removed by compression, this doesn't enable all the liquid to be expelled. It is therefore preferable to remove the liquid phase by a washing step.
The solid material that has been subjected to the hydrolysis step in the reactor 14 is therefore then washed at step 16, for example using an aqueous solution, and/or clean water, as indicated at 15.
The washed material is then dried at step 17 to evaporate excess moisture, and may be further comminuted (not shown) to ensure all the particles small enough to heat up quickly. The material is then introduced into a hopper 18 with a twin screw outlet, and thence into a thermolysis reactor 20 in which the solid material is entrained into a flow of superheated steam at a significantly higher temperature, for example 550° C. The particles of solid material cool the superheated steam while being heated up, and typically reach a final temperature of 370° C. to 450° C. The particles are effectively subjected to a temperature in the range for example 370° C. to 410° C. or 420° C. for a short period which may for example be between 0.4 seconds and 1 second. Under these reaction conditions the cellulose undergoes thermolysis, mainly producing C6 sugar derivatives which are volatile under these conditions. After passing through the thermolysis reactor 20 the particulate material, which at this stage is a solid lignin char 24, may be separated from the vapours and gases by passing through a cyclone 21, and the vapours then condensed in a condenser 22. A fan 23 ensures the through-flow of any uncondensed vapours or steam and any non-condensable gases, such as air entrained in the particulate material.
The condensed vapours create an output stream 25 which is an aqueous solution of the products of degradation or thermolysis of the cellulose, which will primarily consist of C6 sugars, typically in an anhydrous form. For example the products may be anhydroglucose (which is also called levoglucosan), but there may also be phenolic-substituted glucose, and phenolic-substituted anhydrosugars as well as oligomeric anhydrosugars and sugar oligomers.
This output stream 25 of condensed vapours from the cellulose thermolysis reactor 20 may optionally be fed back (not shown), and used in the washing step 16. In that case the resulting aqueous solution 26 contains the C5 sugars produced during hemicellulose hydrolysis, and also the C6 sugars produced during cellulose thermolysis, and at least the latter may be in an anhydrous form. The aqueous solution 26 also contains the bulk of the acid added at step 12 before the biomass was treated in the hemicellulose hydrolysis reactor 14. Alternatively, as indicated in
Referring now to
In operation of the thermolysis reactor 20, particulate material from the hopper 18 is fed at a steady rate of 175 kg/h into the inlet port 34, and steam at 550° C. is supplied at 700 kg/h through the nozzle 36, corresponding to a modulus of 4. This ensures a steam flow at 12 m/s along the reactor duct 30. The steam is supplied to the nozzle at 130 kPa (1.3 bar(a)), generating a pressure reduction of about 2 kPa (20 mbar) below the inlet port 34. The deflector plate 40 ensures the particles do not contact the hot surfaces of the nozzle 36 itself, but fall down under the influence of the pressure reduction, into the jet of steam from the nozzle 36, and are entrained into the flowing steam. The steam pressure within the entry chamber may be 100 kPa (1.0 bar(a)), and at the other end of the reactor duct 30 the steam pressure drops to about 95 kPa (0.95 bar(a)). Arrow A indicates the steam flow, arrow B represents the flow of particulate material, and arrow C represents the resultant flow of these reagents and of thermolysis products.
Referring now to
To monitor and control operation, the steam supply system 42 also includes temperature sensors 49a and 49b to measure the temperature of the steam before and after passage through the superheater 47; and there is also a pressure relief valve 49c which would release pressure if it exceeded a safe value; this may for example be set at 200 kPa (2 bar(a)).
Referring now to
Referring now to
Referring again to
The desired reaction of the thermolysis of cellulose to produce sugars takes place under these conditions very quickly, typically in less than 1 second. If the particulate material is exposed to the reaction conditions (i.e. the high temperature steam) for significantly longer, the lignin will degrade to produce unwanted organic compounds such as phenols, and may also produce tar. It is therefore advantageous to remove the particulate material from contact with the high temperature steam once the desired reaction has taken place. Hence during operation the screw 64 is rotated continuously to transfer any deposited particulate material to the outlet port 66, and the rotary valve 68 is operated continuously to remove any such particulate material and so to prevent further degradation; and similarly the rotary valve 75 at the base of the cyclone 21 is operated continuously to remove the particulate material from the cyclone 21. The rotary valves 68 and 75 significantly inhibit any flow of air into the thermolysis reactor 20 or the cyclone 21.
Operation of the thermolysis reactor 20 leads to the formation of particles of lignin char. Some of these particles may settle out at the end fitting 60, in which case they can be removed through the gate valve 66. Most of the particles are carried along with the high temperature gas and vapour stream along the diverging portion 62, and so are fed through the connecting duct 69 into the cyclone 21. Within the cyclone 21 all but the smallest of particles settle out, so the gas and vapour stream emerging from the cyclone 21 contains only very small particles, if any.
Referring now to
The spray nozzles 84 may be fed either with mains water, indicated by arrow W or by recycled water indicated by arrow R. When operation starts, mains water is used, but during steady-state operation the water is primarily recycled water. The quantity of water sprayed is only enough to cool the steam so that it is saturated. This de-superheating condenser 80 will also tend to trap any particles, which will therefore collect in the bottom portion 86, and can occasionally be withdrawn through the valve 88.
The second condenser 82 is a significantly larger vertical cylindrical chamber, and the de superheated gases and vapours from the first condenser 80, indicated by arrow C, are fed into an inlet port 90 towards the bottom of the chamber, but above the water level 92 during operation. Remaining gases and vapours leave the second condenser 82 from the top, indicated by arrow G, and this flow is ensured by the fan 23 (shown in
The second condenser 82 is provided with three inlet ports 94 spaced apart along its length, each port 94 being a short distance above a horizontal tray 96 within the chamber, each tray 96 being clamped between flanges of tubular elements that form the cylindrical chamber. Each port 94 is closed by an end plate 97 and is provided with a water inlet 98 to feed water onto the tray 96. In operation water is continuously cascading down from the trays 96, so the gas flow is counter current to the falling water. Initially, as indicated by arrow W, the water may be mains water, but during normal operation the water provided to each water inlet 98 is recycled water, indicated by arrow R, which is an aqueous solution of the products produced by the cellulose thermolysis.
During operation the quantity of water provided to the second condenser 82 is such as to ensure that the outgoing gases, indicated by arrow D, remain at a temperature of at least 60° C. Nevertheless the bulk of the steam provided to the thermolysis reactor 20 will be condensed during its passage through the second condenser 82.
An outlet duct 100 connects to the bottom of the chamber, and connects to a pressure sensor 102 and to an outlet valve 104 which is normally closed. The recycled water which is provided to both the spray nozzles 84 and the water inlets 98 is taken from outlet ports 106 near the bottom of the chamber, being recirculated for example by a pump 108. During operation the concentration of the products of thermolysis of cellulose in the aqueous solution will at least initially increase as this solution is recirculated, and the total quantity of water will gradually increase. When the liquid level 92 reaches a preset threshold, as sensed by the pressure sensor 102, a valve 109 is opened so that some of the aqueous solution is transferred to a product storage tank 110.
Referring now to
It has been found that operating at a temperature no lower than 60° C. ensures that any tar that may be present, as a potential product of thermolysis, remains sufficiently fluid that it does not form blockages. It will therefore be carried through into the product storage tank 110 along with the aqueous solution, and can subsequently be separated. Nevertheless, if any blockage of the perforations of a tray 96 occurs, the perforated base plate 118 can be replaced during maintenance by disconnecting the end plate 97 from the port 94, lifting out the base plate 118 through the port 94, and replacing it with a clean base plate 118. It will also be appreciated that both the first condenser 80 and the second condenser 82 have a dead volume below the inlet for gases and vapours, to remove any tar or particulate char material, which ensures that such material does not cause blockages to pipework or pumps downstream.
It will be appreciated that the description above is given by way of example only, and that modifications may be made while remaining within the scope of the invention, which is as defined in the claims. By way of example, the flow diagram of
As described above, the downstream end of the thermolysis reactor 20 is provided with the generally Y-shaped end fitting 60 in order to accommodate the screw 64, as shown in
Number | Date | Country | Kind |
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2002587.0 | Feb 2020 | GB | national |
This application is a 371 National Stage of International Application No. PCT/GB2021/050472, filed Feb. 24, 2021, which claims priority to United Kingdom Patent Application No. GB 2002587.0, Feb. 24, 2020, the disclosures of which are herein incorporated by reference in their entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/GB2021/050472 | 2/24/2021 | WO |