Method for cleaning a reactor for processing a lignocellulosic biomass
12612588 ยท 2026-04-28
Assignee
- Ifp Energies Nouvelles (Rueil-Malmaison, FR)
- Institut National De Recherche Pour L'Agriculture L'Alimentation Et L'Environment (Paris, FR)
- ARGO INDUSTRIES RECHERCHE ET DEVELOPPEMENT (Pomacle, FR)
Inventors
- Meriem BOURAS (Rueil-Malmaison, FR)
- Caroline Aymard (Rueil-Malmaison, FR)
- Olivier CARNNOT (Baccones, FR)
Cpc classification
C12M39/00
CHEMISTRY; METALLURGY
C12M45/04
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to a processing method at acidic or neutral pH in a reactor (4) for processing lignocellulosic biomass (P), said process including a continuous cleaning phase of the reactor which comprises introducing a basic aqueous solution (EB) into said reactor containing the biomass being processed.
Claims
1. A process for treatment of a lignocellulosic biomass (P), said process comprising: impregnating the lignocellulosic biomass (P) with an acidic aqueous solution (EA) in an impregnation reactor (3) to form an impregnated lignocellulosic biomass (P), pretreating the impregnated lignocellulosic biomass (P) in a pretreatment reactor (4), and providing a phase of continuous cleaning of the pretreatment reactor (4) while pretreating the impregnated lignocellulosic biomass (P) in a pretreatment reactor (4), wherein the phase of continuous cleaning comprises: introducing a basic aqueous solution (EB) into said pretreatment reactor (4) containing the impregnated lignocellulosic biomass (P), and adjusting a concentration of the basic aqueous solution (EB) to increase a pH of the impregnated lignocellulosic biomass (P) in the pretreatment reactor (4) from an acidic pH range of between 0.5 and 3, to a basic pH range of between 8 and 14, wherein the pH of the basic aqueous solution (EB) before introduction into the pretreatment reactor (4) is greater than or equal to 9.
2. The process as claimed in claim 1, wherein the basic aqueous solution (EB) is heated before introduction into the pretreatment reactor (4) to a temperature of at least 40 C.
3. The process as claimed in claim 1, wherein the pretreatment reactor, has an internal volume and wherein the temperature of the internal volume of the pretreatment reactor is at least 120 C. when the basic aqueous solution is introduced.
4. The process as claimed in claim 1, wherein the introduction of the basic aqueous solution (EB) into said pretreatment reactor (4) containing the impregnated lignocellulosic biomass (P) has a duration of between 15 minutes and 8 hours.
5. The process as claimed in claim 1, wherein during the phase of continuous cleaning of the pretreatment reactor (4), the basic aqueous solution (EB) has a residence time in said pretreatment reactor (4) of between 5 and 15 minutes.
6. The process as claimed in claim 1, wherein during the phase of continuous cleaning of the pretreatment reactor (4), the basic aqueous solution (EB) is introduced at an inlet of said pretreatment reactor (4) at flow rate, the process as claimed in claim 1, further comprises adjusting the flow rate so that a solids content SC of the lignocellulosic biomass (P) decreases during its passage through the pretreatment reactor from a value of 30% SC to 60% SC.
7. The process as claimed in claim 1 further comprising: introducing a change to at least one of a physical, chemical or rheological characteristic of the impregnated lignocellulosic biomass (P) in the pretreatment reactor (4) during the continuous cleaning phase.
8. The process as claimed in claim 1, wherein pretreating the impregnated lignocellulosic biomass (P) in a pretreatment reactor (4) is achieved by steam explosion cooking, wherein said steam explosion cooking provides steam having thermal energy in the pretreatment reactor (4), the process of claim 1 further comprising: exhausting at least a first portion of the steam at an outlet of a separation device (5) is positioned at an outlet of the pretreatment reactor (4), recovering said thermal energy of the at least first portion of steam via a heat exchanger, and heating one of the basic aqueous solution (EB), an acidic aqueous solution (EA), or a neutral aqueous solution (E), and condensing a second portion of the steam via a condenser.
9. The process as claimed in claim 1, further comprising reducing or eliminating acid content of the acidic aqueous solution (EA).
10. The process as claimed in claim 1, wherein during the phase of continuous cleaning of the pretreatment reactor (4), the acidic aqueous solution (EA) is replaced by the basic aqueous solution (EB), or by an aqueous solution (E) having a neutral pH.
11. The process as claimed in claim 1, wherein the impregnation of the lignocellulosic biomass (P) is realized via a first impregnation reactor (3) and a second impregnation reactor (3) used in parallel, the first impregnation reactor (3) is fed with an acidic aqueous solution (EA) or with an aqueous solution (E) of neutral pH, and the second impregnation reactor (3) is fed with basic aqueous solution (EB), wherein the first impregnation reactor (3) and a second impregnation reactor (3) are operate alternately, and wherein the second reactor (3) is operational during the phase of continuous cleaning the pretreatment reactor (4).
12. The process as claimed in claim 1 further comprising: separating the lignocellulosic biomass (P) and an aqueous phase in liquid or vapor form at an outlet of the pretreatment reactor (4) by a separation device (5), and wherein the phase of continuous cleaning of the pretreatment reactor (4) comprises, at least one rinsing of the separation device by an aqueous solution (E) after introduction of the basic aqueous solution (EB) into the pretreatment reactor (4).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE EMBODIMENTS
(12) The figures are very diagrammatic; the same references correspond to the same components from one figure to another. The reactors are represented in the spatial position which they substantially occupy in the operational position.
(13) The process for cleaning a reactor for the treatment of biomass is illustrated here in the context of a process for the treatment of biomass intended to produce alcohols, in particular biofuel of the bioethanol type, according to the stages of the process according to
(14) It is a pretreatment, in the sense known in the field of the conversion of lignocellulosic biomass. An embodiment of this process is described in more detail, for example, in the patent WO 2018/015227, to which reference will be made if necessary.
(15) It should be noted that the cleaning process according to the invention can be applied in the same way to any reactor for the pretreatment of biomass and more generally to any reactor which is intended to treat a lignocellulosic biomass, the treatment having the object of modifying one of its chemical, physical or rheological characteristics, and generally being operated at high temperature.
(16) The process for the treatment of biomass taken here as an example and represented in
(17) These stages of the process are carried out continuously and are described in detail below using the description of the items of equipment used to implement it: A vessel for preparation 1 of an impregnation liquor containing a chemical catalyst is provided, which liquor is formed from water E and from catalyst A which will feed it; the catalyst in this case is a strong acid of concentrated sulfuric acid type in an aqueous phase, this vessel making it possible to feed the impregnation reactor 3 with a mixture of water E and of chemical catalyst A, A conical screw 2 (also called plug screw or sealing screw) for feeding with fresh biomass (in this instance wheat straw P) into the impregnation reactor 3, A line for feeding the reactor with impregnation liquor connecting the vessel for preparation of liquor 1 and the impregnation reactor 3, An impregnation reactor 3 equipped with two upward transportation screws (not represented) making it possible for the biomass to pass from the impregnation zone in the lower part of the reactor to the draining zone in the upper part of the reactor, and to bring the impregnated and drained biomass to the reactor outlet located at the top of the reactor.
(18) This impregnated and drained biomass is subsequently sent to the pretreatment by a feedline emerging in a second conical screw 2, This second conical screw 2 feeds a pretreatment reactor 4 with impregnated biomass, The pretreatment reactor 4 treats the impregnated biomass by steam explosion, A water circuit for washing the conical screws 2,2 of the impregnation reactor 3 and of the pretreatment reactor 4, represented symbolically in
(19) This must M exhibits at this stage a sufficient accessibility of the cellulose to enzymes to be treated by enzymatic hydrolysis for the production of 2G sugars. The conditions of the enzymatic hydrolysis and of the consecutive or simultaneous fermentation which follow this separation (not represented in
(20) The use of the pretreatment technique described above results in the deposition of different types of biomass (wheat straw here, but also miscanthus, poplar, and the like), which accumulate at/adhere to the surface of at least one of the transportation screws internal to the pretreatment reactor 4. These deposits undergo a cooking over times longer than the normal residence time of the biomass in the reactor, and are transformed into a residue, which can be called coke here. This coke can create various operating problems, such as blockages of the outlet orifice of the reactor 4 or an increase in the frictional actions of the transportation screw(s) in question on the wall of the chamber in which they are housed, and this may result in a reduction in the performance characteristics of the pretreatment unit in its entirety as represented in
(21) The definition of the composition of the coke has proven to be problematic because it concerns a residue, the appearance and the composition of which change over time: at the start of a production cycle, the material which is deposited is biomass; it thus has essentially the same characteristics as the biomass which continues its journey through the reactor 4 and toward the downstream stages. The deposit which is formed by adhesion to the internal wall of the reactor 4 will remain for a much longer time under the cooking conditions (temperature in particular) than desired. The effect of the temperature affects the composition and the morphology of the residue, which will change toward an increasingly cooked residue. The more the residue is cooked, the more compact it is and the more it adheres to the walls of the reactor.
(22) These coke deposits are cumulative: the longer the continuous operating time of the tool, the greater the amount of coke deposited, and the more the layers of coke close to the wall will change toward a very hard solid. These deposits thus bring about a fouling phenomenon, by increasing the thickness of the walls and by reducing the useful volume of the reactor. Depending on the configuration of the cooking reactor, and in particular the type of internal in place, there may be observed interference with the rotation of certain elements, such as the screw, or one at least of the screws for transportation of the biomass in the reactor being cooked. This interference is observed in particular by an increase in the power of the motor rotating the screw.
(23) Throughout the production, it can also happen that a part of this residue, which is more or less hardened, detaches from the wall of the reactor, under the effect, for example, of the rotation of the screw or of one at least of the transportation screws internal to the reactor or of the passage of the biomass through the reactor: thus, particles with a much greater density than the bed of biomass being cooked can be caused to detach and to be entrained toward the outlet orifice of the reactor, which can generate blockages or operating problems downstream. Despite these detachments, it is found that the deposits continue to increase over time during a given production cycle.
(24) After stopping, cooling and opening the cooking reactor 4, it could be found that the coke exists in two forms: a hard form in direct contact with the internal walls of the reactor and a more friable form which covers the hard coke. The difference between these two cokes is found in their elemental compositions, as shown in table 1 below.
(25) TABLE-US-00001 Friable coke Hard coke Carbon content (%) 44.57 65.07 Hydrogen content (%) 5.85 4.67 Oxygen content (%) 34.63 24.58
(26) It is observed that the percentage of carbon contained in hard coke is higher than that in friable coke, while an opposite trend is noted for the oxygen content, and similar values are noted for the hydrogen content. It emerges from this that friable coke is, as it were, the precursor of dense coke.
(27) The invention consists in continuing the operation of the two impregnation 3 and pretreatment 4 reactors, while carrying out the chemical cleaning of the reactor 4 in order to extract this coke C and/or to slow down its formation.
(28) This cleaning does not require the opening of the reactor and the mechanical cleaning of the interior of the reactor, as was the case previously. This cleaning according to the invention, described in detail below, is thus faster, more economical and safer, since it makes it possible to limit the operating risks associated with the assembling and dismantling of the unit and, above all, since it makes it possible not to stop the production.
(29) An example of implementation of the process according to the invention and its alternative forms are explained with the help of the combined figures. It requires the following additional items of equipment, with respect to those already described, in the light of
(30) The course of the implementational example of the cleaning process according to the invention comprises two consecutive sequences: Sequence 1: Injection of the preheated basic liquor EB into the reactor 4 while the reactor is being fed with the acidic biomass.
(31) The injection conditions are as follows: the basic solution EB is an aqueous KOH solution, with a KOH concentration of 1% to 50% by weight of KOH, preferably from 5% to 12% by weight of KOH, with respect to the water the flow rate of the solution EB into the reactor is between 100 and 500 kg/h, in particular approximately 300 kg/h the degree of filling by the biomass impregnated with the basic solution EB of the reactor 4 is from 20% to 90%, in particular approximately 30% the temperature at which the solution EB is injected into the reactor 4 is between 80 C. and 200 C., in particular approximately 130 C. the temperature of the reactor 4 is between 150 C. and 220 C., in particular approximately 200 C. the duration of this sequence is between 15 minutes and 8 hours; it is in particular 2 hours the residence time of the solution EB in the reactor 4 is between 5 and 15 minutes, and in particular approximately 10 minutes. Sequence 2: Cleaning the cyclone 5 by rinsing with the water ER to complete the cleaning. The term water flush can be used, insofar as the rinsing consists, in this implementational example, in spraying water under pressure into the cyclone, which water is subsequently rapidly discharged.
(32) The operating conditions for this sequence are as follows: number of rinsing operations: from 1 to 10, for example equal to 2 temperature of the rinsing water: 20 C. to 80 C., for example 20 C. (i.e. either a temperature at ambient or close to ambient, or a higher temperature requiring preheating of the rinsing water ER)
(33) In the cleaning phase, a must is obtained at the outlet of the cyclone 5 which is no longer the conventional acidic must M but a basic must M1.
(34) The frequency of the cleaning procedure can vary widely depending on the type and size of the pretreatment reactor 4, on the type of biomass being treated, and the like. For example, the cleaning can be triggered when the torque of one of the transportation screws internal to the reactor increases by more than 15%, with respect to the torque observed at the start of production. It can also be triggered after a given period, which can range from 2 hours to 4 months of production.
(35) Different alternative forms can be introduced to the example of cleaning process described above, while remaining within the scope of the invention, some of which are described in detail below (some at least of these alternative forms can be alternative or cumulative):
(36) ADuring cleaning, the concentration of acid A of the vessel for preparation 1 of the impregnation liquor can be reduced to a zero concentration optionally, that is, ultimately, an impregnation which is carried out only with water.
(37) BThe aqueous washing liquor E for the screw 2 (which is neutral) bringing the impregnated biomass into the reactor 4 can be recycled into the vessel for preparation 6 of the basic solution EB during the cleaning, which makes it possible to reduce the additional water consumption due to the cleaning, as represented in
(38) CThe biomass can be impregnated with a basic liquor during the cleaning sequence, either with the same basic liquor EB as that prepared in the vessel 6 or a different basic liquor, in particular in terms of concentration of base B. This alternative form makes it possible to reduce the amount of pure basic solution to be introduced into the pretreatment reactor 4, since there will no longer be, or will be less, acid to be neutralized in order to reach the targeted basic pH. However, a certain amount of basic liquor will be removed in the pressate (which corresponds to the water extracted from the screw 2).
(39) Thus, it may still be necessary to top up with basic liquor EB directly in the reactor 4 (via the vessel 6).
(40)
(41) The vessel 6 can thus simultaneously feed the two reactors 3 and 4, or at least for a common period during the cleaning of the reactor 4. It is also possible to anticipate and begin to feed one of the reactors with basic solution EB before the other, in particular the impregnation reactor 3 before the start of cleaning by the solution EB of the pretreatment reactor 4.
(42) DIt is also possible to combine the two preceding alternative forms, as represented in
(43) EIt is also possible to use two impregnation reactors 3,3 operating alternately, as represented in
(44) FThe alternative forms E and B can be combined, that is to say the two impregnation reactors 3,3 can be used and the water extracted from the screw 2 can be recycled in the vessel 6 for preparation of basic liquor EB.
(45) GThe must (also called marc) can be recycled, in particular in the context of the alternative form E having two impregnation reactors: the basic pretreated biomass M1 which exits from the separation device 5 during the cleaning of the pretreatment reactor 4. This is because, during this period, it is basic. It is then possible to wash this must M1 at the outlet of the separation device 5 with water: it becomes a washed basic must M1, as represented in
(46) HAnother alternative form consists in using two separation devices 5,5 (cyclone) operating alternately, as represented in
(47) JThis alternative form emerges from the preceding alternative form E having two impregnation reactors 3,3, with the following difference: In production mode, use is made of the conventional impregnation reactor 3 fed with acidic solution EA by the vessel 1. In production+cleaning mode, the system is switched here to the second impregnation reactor 3 which is fed only with water, as represented in
(48) KThe invention also applies to processes for the pretreatment of biomass without prior preimpregnation with a liquor (reference is then made to self-hydrolysis): in this case, the biomass P, after having optionally undergone a treatment of mechanical (grinding, and the like), thermal (drying) or humidification type, is introduced directly into the pretreatment reactor 4, as represented in
(49) LThis alternative form, illustrated in
(50) MThis alternative form, represented in
(51) NAccording to another alternative form, it is possible to choose to inject biomass impregnated with acidic liquor EA into the pretreatment reactor 4 from the impregnation reactor 3 in production mode, and to directly inject the nonimpregnated biomass P into the pretreatment reactor 4 in production+cleaning mode, by then stopping the feeding of biomass impregnated with acidic liquor.
(52) OAccording to yet another alternative form, which can be combined with all the others, it is possible to choose to inject, into the pretreatment reactor, a given impregnated biomass in production mode and to inject another biomass, impregnated or not with a liquor, in production+cleaning mode. For example, in production, a straw-type biomass is chosen and, in production+cleaning mode, a more abrasive poplar-based biomass is chosen: a temporary increase is thus brought about in the cleaning time, the abrasive nature of the biomass, in order to help to more easily detach solid coke residues from the walls.
EXAMPLES
Example 1 not in Accordance with the Invention
(53) It uses the configuration presented in
(54) It concerns a mechanical cleaning of the pretreatment reactor with stopping of the production and opening of the reactor, according to an earlier solution.
(55) It was carried out with wheat straw as biomass. The characteristics and composition of the feedstock are as follows: Solids content: 91.07% Biomass flow rate: 65 kg SC/h
(56) The operating conditions for producing pretreated biomass are as follows: Impregnation for the production in the impregnation reactor 3:
(57) Acidic H.sub.2SO.sub.4 solution flow rate: 1.5 kg/h (pH of approximately 1) Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(58) Residence time: 5 min
(59) Production duration: 72 hours Mechanical cleaning according to prior art:
(60) Temperature drop time: 48 hours
(61) Opening and dismantling time: 8 hours
(62) Cleaning time: 8 hours
(63) Time for reassembling the reactor: 8 hours
(64) The weight of coke C produced is 16 kg occupying a volume of 0.012 m.sup.3 in the reactor 4, i.e. a reduction in the reactor volume of 8.7% and a coke production throughput of 222 g/h.
Example 2 in Accordance with the Invention
(65) It uses the configuration presented in
(66) The characteristics and composition of the wheat straw feedstock are identical to those of the wheat straw used in example 1.
(67) The operating conditions are described in detail below:
(68) Mode 1=production: Impregnation for the production in the impregnation reactor 3:
(69) Acidic solution flow rate: 1.5 kg/h (H.sub.2SO.sub.4) Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(70) Residence time: 5 min
(71) Production duration: 20 hours
(72) The pressate E1 resulting from the screw 2 is completely recycled to the vessel 1 for preparation of the acidic aqueous solution.
(73) After 20 hours of production, the cleaning sequence is carried out under the following conditions:
(74) Mode 2=production+cleaning: Impregnation in the impregnation reactor 3:
(75) Acidic solution flow rate (acidic solution EA): 1.5 kg/h (H.sub.2SO.sub.4) Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(76) Residence time: 10 min
(77) Temperature in the reactor: 200 C.
(78) KOH flow rate: sufficient to lower the SC down to the saturation value of the biomass Duration of the cleaning: 2 hours
(79) Concentration of KOH in the liquor: sufficient to change the biomass from a pH of 3 to a pH of 13
(80) Number of cycles: 3 cycles of mode 1 (production) and of mode 2 (production+cleaning) Cleaning of the cyclone 5 (separation device)
(81) Number of water flushes: 2, after each cleaning operation
(82) After 3 cycles of mode 1+mode 2, for a total production duration of 66 h (60 hours of production and 6 hours of cleaning), the cleaning proved to be effective.
(83) This is because the weight of coke C recovered at the end of the procedure (thus after these 3 cycles) does not exceed 3 kg, i.e. a coke production throughput of 39 g/h.
(84) Thus, the cleaning procedure made it possible to reduce the production throughput from 222 g/h in 72 hours to only 39 g/h after a production of 60 h separated from 3 cleaning operations each of 2 hours.
Example 3 in Accordance with the Invention
(85) It is identical to example 2 except that the production does not last 20 hours but 80 hours. After 3 production and cleaning cycles for a total operating time of 246 hours (240 hours of production mode and 6 hours of production+cleaning mode), the cleaning proved to be effective.
(86) This is because the weight of coke C recovered at the end of these three cycles does not exceed 3 kg, i.e. a coke production throughput of 41 g/h.
(87) Thus, the cleaning procedure made it possible to reduce the production throughput from 222 g/h in 72 h to only 41 g/h after a production of 240 hours separated from 3 cleaning operations each of 2 hours.
Example 4 in Accordance with the Invention
(88) The feedstock is still wheat straw, the characteristics and composition of which are as follows: Solids content: 88.30% by weight Biomass flow rate: 65 kg SC/h
(89) The operating conditions are described in detail below:
(90) Mode 1=production: Impregnation for the production in the impregnation reactor 3:
(91) Acidic solution flow rate: 1.5 kg/h Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(92) Residence time: 5 min
(93) Production duration: 80 hours
(94) After 80 hours of production, the cleaning sequence is set in motion under the following conditions:
(95) Mode 2=production+cleaning: Impregnation in the impregnation reactor 3:
(96) Acidic solution flow rate: 1.5 kg/h Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(97) Residence time: 10 min
(98) Temperature of the reactor: 200 C.
(99) KOH flow rate: sufficient to lower the SC down to the saturation value of the biomass
(100) Duration of the cleaning: 2 h
(101) Concentration of the KOH in the liquor: sufficient to change the biomass from a pH of 3 to a pH of 13
(102) Number of cycles: 8 cycles of mode 1 (production) and of mode 2 (production+cleaning) Cleaning of the cyclone 5
(103) Number of water flushes: 2
(104) After these 8 cycles, for a total operating time of 656 hours (640 hours of production and 16 hours of production+cleaning), the cleaning proved to be effective.
(105) This is because, in total, 14.96 kg of coke C were recovered, i.e. a coke production throughput of 22 g/h.
Example 5 in Accordance with the Invention
(106) It was carried out with SRC poplar wood, the characteristics and composition of which are as follows, with the configuration of
(107) Mode 1=production: Impregnation for the production in the impregnation reactor 3:
(108) Acidic solution (2.5% by weight) flow rate: 2.7 kg/h Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(109) Residence time: 7.5 min
(110) Production duration: 60 hours
(111) After 60 hours of production, the cleaning sequence is set in motion under the following conditions:
(112) Mode 2=production+cleaning: Impregnation in the impregnation reactor 3:
(113) Acidic solution (2.5% by weight) flow rate: 2.7 kg/h Steam explosion of the impregnated biomass in the pretreatment reactor 4:
(114) Residence time: 7.5 min
(115) Temperature of the reactor: 200 C.
(116) KOH flow rate: sufficient to lower the SC down to the saturation value of the biomass Duration of the cleaning: 2 h
(117) Concentration of the KOH in the liquor: sufficient to change the biomass from a pH of 3 to a pH of 13
(118) Number of cycles: 3 cycles of mode 1 and of mode 2 Cleaning of the cyclone 5 Number of water flushes: 2
(119) After these 3 cycles, for a total operating time of 186 hours (180 hours of production and 6 hours of cleaning), the cleaning proved to be effective.
(120) This is because, in total, 8 kg of coke were recovered, i.e. a coke production throughput of 121 g/h.
(121) In conclusion, the cleaning according to the invention avoids having to stop the production, with all the disadvantages which are connected with this (loss of time, loss of yield, more burdensome servicing by operators), or, at the very least, makes it possible to very significantly space out the complete cleaning operations with stopping of production.