Lignocellulosic biomass processing method
阅读说明:本技术 木质纤维素生物质处理方法 (Lignocellulosic biomass processing method ) 是由 C.艾马尔 P-A.布永 M.布拉加利尼 于 2018-12-04 设计创作,主要内容包括:本发明涉及处理固含量不大于80重量%的木质纤维素生物质的方法,所述方法包括使用至少一个反应器(9,14)来处理所述生物质,其中所述反应器或所述反应器中的至少一个经由进料设备(6,11)来进料生物质,所述进料设备(6,11)在所述进料设备的生物质入口和生物质出口之间产生压力升高,其中通过洗涤流体在洗涤入口(7,12)和洗涤出口(8,13)之间的循环来洗涤所述进料设备。根据所述方法,将离开至少一个进料设备(6,11)的流体出口的洗涤流体(8,13)的至少一部分重新引入同一进料设备或所述进料设备中的另一个的洗涤入口中。(The invention relates to a method for treating lignocellulosic biomass having a solids content of not more than 80 wt.%, comprising treating the biomass using at least one reactor (9, 14), wherein the reactor or at least one of the reactors is fed with biomass via a feeding device (6, 11), the feeding device (6, 11) generating a pressure increase between a biomass inlet and a biomass outlet of the feeding device, wherein the feeding device is washed by circulation of a washing fluid between a washing inlet (7, 12) and a washing outlet (8, 13). According to the method, at least a portion of the scrubbing fluid (8, 13) exiting the fluid outlet of at least one feed device (6, 11) is reintroduced into the scrubbing inlet of the same or another of the feed devices.)
1. Method for treating lignocellulosic biomass having a solids content of not more than 90% by weight, the method comprising treating the biomass using at least one reactor (9, 14), wherein the reactor or at least one of the reactors is fed with biomass via a feeding device (6, 11), the feeding device (6, 11) generating a pressure increase between a biomass inlet and a biomass outlet of the feeding device, wherein the feeding device is washed by circulation of a washing fluid between a washing inlet (7, 12) and a washing outlet (8, 13), characterized in that at least a part of the washing fluid leaving the fluid outlet of the feeding device or at least one of the feeding devices (6, 11) is reintroduced into the washing inlet of the same feeding device or the other of the feeding devices.
2. The method as claimed in the preceding claim, characterized in that liquid is extracted from the biomass during the passage of the biomass through the or one of the feed devices (6, 11).
3. The method as claimed in one of the preceding claims, characterized in that the pressure increase produced in the feed device or in at least one of the feed devices (6, 11) is at least 0.05MPa, in particular 0.05-4 MPa.
4. The method according to one of the preceding claims, characterized in that it comprises a step of impregnating the biomass with an impregnation liquid containing a chemical catalyst by introducing the biomass into the reactor or one of the reactors (9, 1) equipped with a feeding device (6, 11).
5. The method according to any one of claims 1 to 4, characterized in that the method comprises the step of impregnating the biomass with an impregnation liquid containing a chemical catalyst by passing the biomass through a liquid bed, or by spraying the biomass with the liquid on a belt conveyor (9'), or by passing the biomass through an agitated reactor.
6. The method according to any one of claims 1 to 4, characterized in that the method comprises the step of impregnating the biomass with an impregnation liquid containing a chemical catalyst and introducing the biomass into a reactor (9) via the feeding means or at least one of the feeding means (6).
7. The method as claimed in one of the preceding claims, characterized in that the method comprises a step of treating the biomass by cooking, in particular in the reactor or one of the reactors (14) provided with a feed device (11).
8. The method according to one of the preceding claims, comprising the steps of:
a. preparing in a preparation zone (3) an impregnation liquor (4) comprising a chemical catalyst (2) intended for impregnating the biomass (5), the chemical catalyst being selected from the group consisting of acid catalysts, basic catalysts and oxidation catalysts, preferably acid catalysts;
b. introducing ground biomass (5) via an inlet of an impregnation reactor (9) by means of a first feeding device (6) which is washed by circulation of a first washing fluid (7, 8) between the inlet and the outlet of the device (6);
c. introducing liquid into the impregnation reactor (9) via the first liquid (4) inlet of the reactor;
d. transferring the impregnated and drained biomass (10) from the impregnation reactor outlet to the inlet of a digestion pretreatment reactor (14), introducing it into the pretreatment reactor via a second feeding means (11), washing the second feeding means by circulation of a second washing fluid (12, 13) between the inlet and the outlet of the feeding means;
e. pretreating the biomass (10) in the steam explosion reactor (14);
f. reintroducing at least a portion of the first and/or second washing fluid exiting the fluid outlet of the first or second feeding device (6, 11) into the washing inlet of the first feeding device (6) and/or second feeding device (11).
9. The method of the preceding claim, wherein the method further comprises:
g. reintroducing a portion of the first and/or second washing fluid leaving the fluid outlet of the first or second feeding device (6, 11) into the impregnation liquid preparation zone (3) for a) preparing the liquid.
10. The method according to one of the preceding claims, characterized in that the feeding device and/or at least one of the feeding devices is a feeding screw (6, 11), which is in particular at least partially conical, comprising a hood equipped with a grid enabling circulation of the washing fluid and optionally extraction of the fluid from the biomass.
11. The method according to claim 7 or claim 8, characterized in that a part of the first washing fluid (8) at the washing outlet of the first feeding means (6) is reintroduced into the washing inlets (8b, 8d) of the first feeding means or second feeding means and another part of the washing fluid is reintroduced (8c) into the liquid preparation zone (3) for preparing the liquid.
12. The method according to claim 7 or claim 8, characterized in that a part of the second washing fluid (13) at the washing outlet of the second feeding device (11) is reintroduced into the washing inlets (13b, 13d) of the first or second feeding device (6, 11) and another part (13c) of the washing fluid is reintroduced into the liquid preparation zone (3) for preparing the liquid.
13. The method as claimed in one of the preceding claims, characterized in that the washing of the feed device (11) is carried out in the presence of biomass supplemented with a catalyst, in particular an acidic catalyst, a basic catalyst or an oxidation catalyst, the washing fluid leaving the fluid outlet of the feed device (6, 11) contains a certain content of the catalyst when extracting liquid from the biomass by passing the biomass through the feed device, and the washing fluid containing the catalyst is at least partially reintroduced into the washing inlet of the other of the same feed device or the feed device, which in particular conveys the catalyst-free biomass.
14. Plant for carrying out the process according to one of the preceding claims, characterized in that it comprises at least one reactor for treating lignocellulosic biomass having a solids content of not more than 90% by weight, wherein biomass is fed to the reactor or to at least one of the reactors via a feeding device which generates a pressure increase between a biomass inlet and a biomass outlet of the feeding device, the feeding device is washed by circulation of a washing fluid between a washing inlet and a washing outlet, and means for reintroducing at least a part of the washing fluid (8, 13) leaving the fluid outlet of the feeding device or at least one of the feeding devices (6, 11) into the washing inlet of the other of the same feeding device or feeding device.
15. An apparatus for treating lignocellulosic biomass, comprising:
-a zone (3) equipped with a liquid outlet for preparing an impregnation liquid (4) comprising a chemical catalyst for impregnating the biomass (5), said chemical catalyst being selected from an acid catalyst, a basic catalyst or an oxidation catalyst, preferably an acid catalyst;
-an impregnation reactor (9) equipped with a biomass inlet and a biomass outlet;
-a first device (6) feeding ground biomass to the impregnation reactor (9) via the biomass inlet of the impregnation reactor;
-means for feeding an impregnation liquid (4a) to the reactor (5), said means connecting the liquid outlet of the liquid (4) preparation zone (3) to the first liquid inlet in the impregnation reactor;
-a reactor (14) for pre-treating the impregnated biomass (10) by cooking, the biomass inlet of the reactor being connected to the biomass outlet of the impregnation reactor (9);
-a second device (11) feeding impregnated biomass (10) into the pretreatment reactor (14) via a biomass inlet of the pretreatment reactor;
-circulation of a washing fluid (7, 8) between the inlet and the outlet of the first feeding device (6) of the ground biomass (5) of the impregnation reactor (9);
-circulation of a washing fluid (12, 13) between the inlet and the outlet of the second feeding means (11) of the impregnated biomass (10) of the pretreatment reactor (14);
characterized in that the device further comprises:
-means for reintroducing at least a portion of the first and/or second washing fluid leaving the fluid outlet of the first or second feeding means (6, 11) into the washing inlet of the first and/or second feeding means.
16. Use of the method or device of one of the preceding claims for treating lignocellulosic biomass (5), such as wood, straw, agricultural residues and all dedicated energy crops, in particular annual or perennial plants, such as miscanthus, to produce sugars, biofuels or bio-based molecules.
Technical Field
The present invention relates to a process for treating lignocellulosic biomass to produce "second generation" (2G) sugar liquors. These sugar solutions can be used to produce other products (e.g., alcohols such as ethanol, butanol, or other molecules, e.g., solvents such as acetone, etc.) via biochemical pathways. The process typically comprises three steps, namely liquid (liquor) preparation, impregnation of the biomass and pretreatment of the impregnated biomass, e.g. by cooking, optionally combining cooking with steam explosion.
Prior Art
Lignocellulosic biomass represents one of the most abundant renewable resources on earth. The substrates considered are very diverse and they relate to woody substrates, such as various woods (hardwood and softwood), by-products resulting from agriculture (wheat straw, corn cobs, etc.) or from other industries of agro-food, paper, etc.
The process for biochemical conversion of lignocellulosic material into a 2G sugar liquor comprises in particular a pretreatment step and a step of enzymatic hydrolysis with an enzyme mixture (cocktail). These methods also typically include an impregnation step prior to pretreatment. The sugar liquor resulting from the hydrolysis is then treated, for example by fermentation, and the process further comprises a separation step and/or a purification step of the final product.
Lignocellulosic biomass is composed of three main polymers: cellulose (35% -50%), which is a polysaccharide consisting essentially of hexoses; hemicellulose (20% -30%), which is a polysaccharide consisting essentially of pentoses; and lignin (15% to 25%), which is a polymer having a complex structure and a high molecular weight, composed of aromatic alcohols connected via ether bonds. These different molecules are responsible for the intrinsic properties of the plant wall and organize themselves into complex tangles.
Among the three basic polymers constituting lignocellulosic biomass, cellulose and hemicellulose are basic polymers capable of producing 2G sugar liquor.
Typically, during pretreatment, hemicellulose is mainly broken down into sugars, and cellulose is converted to glucose by enzymatic hydrolysis. However, for enzymes, it is difficult to access the crude cellulose, and thus pretreatment is required. This pretreatment can alter the physicochemical properties of the lignocellulosic material, thereby improving the accessibility of the cellulose to enzymes and its reactivity to enzymatic hydrolysis.
There are many techniques for implementing this pretreatment that are advantageous to the present invention, which will be hereinafter classified under the generic term "cooking": acid cooking, alkaline cooking, steam explosion and organic solvent pulping. The latter method involves pretreatment in the presence of one or more organic solvents and usually water. The solvent may be an alcohol (ethanol), an acid (e.g. acetic acid or formic acid) or acetone. The "organosolv pulping" process results in at least partial dissolution of lignin and partial dissolution of hemicellulose. Thus, there are two exit streams: a pretreated substrate with residual cellulose, hemicellulose and lignin, and a solvent phase containing dissolved lignin and a portion of the hemicellulose. There is usually a regeneration step of the solvent, which can extract the lignin stream. Certain "organic solvent pulping" processes (particularly with ethanol) and the addition of strong acids (e.g., H)2SO4) And (4) combining. It is also conceivable to contact the biomass with a solvent via an impregnation reactor before the digestion stage, or with an acidic catalyst before carrying out "organosolv pulping" digestion.
For example, various configurations are reported in the documents "Production of biological from biochemical materials: A review", M. Balat, Energy Conversion and management 52 (2011) 858-875, or in the documents "biological Production from biological costs: an overview", N. Sarkar, S. Kumar show, S. Banner jee, K.Aikat, recoverable Energy 37 (2012) 19-27.
One of the most effective pretreatments is acid steam explosion, which allows almost complete hydrolysis of the hemicellulose and significantly improves the accessibility and reactivity of the cellulose to the enzymes. One or more further treatments may be performed prior to this pre-treatment.
All these pretreatments apply to the biomass initially in solid form: the purpose of the pretreatment is to destroy their structure.
One of the most effective pretreatments is steam explosion, which allows almost complete hydrolysis of the hemicellulose and significantly improves the accessibility and reactivity of the cellulose to the enzymes. One or more further treatments may be performed prior to this pre-treatment.
Patents US-8057639 and US-8512512 propose a process comprising a first step of hydrolysis of hemicelluloses into C5 sugars under mild conditions, which thus protect them from degradation. This step is carried out in the first reactor by injecting steam at a pressure of 1.5 bar or more, at a temperature of 110 ℃ or more, and optionally in the presence of a weak acid. After this step, washing is carried out to extract and recover the C5 sugar liquor, and then the remaining biomass, rich in cellulose and lignin, is sent to the second step (second reactor) where steam explosion takes place. By injecting high pressure steam, which results in a sudden expansion of the biomass (steam explosion), the second reactor is operated at a higher pressure than the first reactor.
Patent application WO-2013/141776 in the field of papermaking describes an impregnation process in a vertical reactor (impregnator) containing an alkaline impregnation liquid, which reactor thus defines a first zone in which the impregnation is carried out. The lignocellulosic material is received at the bottom of the impregnator and transferred to the top of the impregnator by means of two conveying screws. During its transfer to the second zone of the impregnator, which is located above the liquid level, the biomass is drained off and the liquid falls back into the first zone. In this configuration, the liquid level is controlled by introducing an alkaline liquid.
When the treatment requires pressure steps (impregnation, cooking type pre-treatment, etc.), it is necessary to use solid biomass introduction devices compatible with these pressure steps. For example, in the case of a compression screw, one embodiment thereof is described in patent application CA 277322.
It is therefore an object of the present invention to improve lignocellulosic biomass processing. The object of the invention is in particular to improve the introduction of biomass into a reactor in which one or more biomass treatment steps are carried out.
The object of the present invention is more particularly to improve the biomass impregnation step and the steam explosion step as described in the above mentioned prior art documents. It is a further object of the invention to make the treatment process, in particular both steps, more efficient in terms of energy and/or treatment fluid consumption.
Throughout this text, the abbreviation "SC" denotes the solid content, determined according to the Standard ASTM E1756-08(2015), "Standard Test Method for Determination of Total Solids in Biomass".
Summary of The Invention
The subject of the invention is firstly a method for treating lignocellulosic biomass or lignocellulosic substrates having a solids content SC of not more than 90% by weight, comprising treating the biomass using at least one reactor, wherein the reactor or at least one of the reactors is fed with biomass via a feeding device which generates a pressure increase between a biomass inlet and a biomass outlet of the feeding device, wherein the feeding device is washed by circulation of a washing fluid between a washing inlet and a washing outlet.
According to the invention, at least a portion of the scrubbing fluid exiting the fluid outlet of at least one of the feed devices or the feed devices is reintroduced into the scrubbing inlet of the other of the same feed device or the feed device.
According to the invention, the term "lignocellulosic biomass with a solids content of X%" means a biomass which naturally has a solids content of X% ("natural" biomass) or has this content after one or more operations preceding the process according to the invention.
In fact, it has proved very advantageous to "recycle" all or part of the washing water of the feeding device, which may be, for example, a feeding screw: at least when the biomass does not contain any catalyst, the consumption of washing fluid (water) is saved. Energy savings can also be achieved when the wash water has to be heated before it is introduced into the wash loop, since the "spent" fluid, which already has a temperature above room temperature, is then re-injected into the wash loop. In addition, when it is necessary to wash the feeding device of the biomass supplemented with catalyst (for example after an operation of impregnation with a catalytic liquid using an acidic, basic or oxidative catalyst), it turns out that the washing water leaving the feeding device may contain a certain amount of catalyst (when the biomass has undergone liquid extraction through the feeding device), but the presence of such "spent" washing water also containing catalyst at the inlet of the washing circuit does not constitute any problem.
It should be noted that the implementation of the invention is simple: the apparatus need only envisage one or more additional lines to ensure a direct fluid connection between the washing outlet and the washing inlet of the same feeding device or between the washing outlet of one feeding device and the inlet of another device.
According to the invention, the possibility of draining an optional part of the leaving unrecirculated washing water can also be retained.
The lignocellulosic biomass treated according to the invention has a solids content SC of between 5% and 80% by weight. Preferably, it comprises no more than 75 wt.%, in particular no more than 70 wt.% or 65 wt.%, and in particular less than 50 wt.% solids.
Thus, the biomass treated according to the invention preferably has a certain water content before being introduced into the feeding device. This water may be naturally occurring, as is the case, for example, with biomass in the form of wood chips. It may also be present naturally in very low or very low amounts, as is the case for example with wheat or corn stover. If the moisture content is too low, the biomass can be pre-humidified to achieve a solids content of no greater than 90% or no greater than 80%, which is desirable for the practice of the present invention.
The feeding device according to the invention brings the biomass into a compressed state, the purpose of which is usually to introduce the biomass into a certain zone (reactor) at a higher pressure. This compression, which is generated by the pressure increase in the feeding means, may result in at least a part of the liquid contained in the biomass being extracted or squeezed out, which part of the liquid is optionally mixed with the washing fluid at the fluid outlet from the feeding means. Thus, during the passage of the biomass through the feeding device or one of the feeding devices, at least a portion of the liquid contained in the biomass may optionally be extracted, as a result of the selection of the biomass feeding device.
Thus, if the solids content of the biomass is high, at the upper limit of the above range (e.g., about 70% or 75% -90%), little or no fluid is extracted from the biomass of the extraction device through the wash fluid outlet, and the present invention particularly allows for the recycle of wash fluid for injection into the feed device.
In addition, if the solids content is low, at the lower limit of the above range (for example below 70%, below 65% or even below 50%), a certain amount of fluid will be extracted from the biomass, whereby the invention may further reduce the supply of washing fluid, or even eliminate the need for supplying washing fluid, whereby washing can be performed wholly or partly with the fluid extracted from the biomass.
Preferably, the lignocellulose substrate thus leaving the feeding device has a solid content SC of greater than or equal to 20 wt%, preferably greater than or equal to 40 wt%.
Preferably, the pressure increase generated in the feeding means or in at least one of the feeding means is at least 0.05MPa, in particular 0.05-4MPa, such as 0.1-2.5 MPa.
The feeding device or devices (for example in the form of a feeding screw), in particular at least partially conical, comprise a hood equipped with a grid for circulating the washing fluid. Typically, the conical shape of the end portion of this type of helix will thus compress the biomass, thereby creating a pressure differential. This type of feeding device has one major advantage: the spiral may form a sealed plug of biomass, which ensures tightness and significantly prevents any liquid from gushing out of the reactor in which it is located.
An example of this type of helix is described in document CA 277322.
Thus, the present invention may be applied to any treatment of biomass in a reactor using a pressurized biomass feed device, in particular any treatment at a pressure above atmospheric pressure or above the pressure of the biomass prior to introduction into the reactor.
According to one embodiment, the method of the invention comprises the step of impregnating the biomass with an impregnation liquid containing a chemical catalyst. This step may be followed (directly or by envisaging one or more intermediate steps) by a cooking step carried out by said reactor or one of said reactors equipped with feeding means.
According to one embodiment, the method of the invention comprises the step of impregnating the biomass with an impregnation liquid containing a chemical catalyst by passing the biomass through a liquid bed, or by spraying the biomass with the liquid on a belt conveyor, or by passing the biomass through an agitated reactor.
According to another embodiment, the method of the invention comprises the step of impregnating the biomass with an impregnation liquid containing a chemical catalyst and by introducing into the reactor via the feeding means or at least one of the feeding means.
According to one embodiment, the process of the invention comprises a step of treating the biomass by cooking, in particular in said reactor or one of said reactors equipped with a feeding device.
An example of a method for carrying out the invention is as follows: treating lignocellulosic biomass, the method comprising the steps of:
a. preparing in a preparation zone an impregnation liquor comprising a chemical catalyst intended for impregnation of the biomass, the chemical catalyst being selected from the group consisting of an acidic catalyst, a basic catalyst and an oxidation catalyst, preferably an acidic catalyst;
b. introducing the ground biomass via the inlet of the impregnation reactor by means of a first feeding device, washing said first feeding device by circulation of a first washing fluid between the inlet and the outlet of said device;
c. introducing a liquid into the impregnation reactor via a first liquid inlet of the reactor;
d. transferring the impregnated and drained biomass from the outlet of the impregnation reactor to the inlet of a digestion pretreatment reactor, introducing it into the pretreatment reactor via a second feeding means, washing the second feeding means by circulation of a second washing fluid between the inlet and the outlet of the feeding means;
e. pretreating the biomass in the digestion reactor.
Furthermore, the method may comprise one or more of the following steps:
f. reintroducing at least a portion of the first and/or second wash fluid exiting the fluid outlet of the first or second feed device into the wash inlet of the first and/or second feed device.
Preferably, the impregnation and steam cooking pretreatment are carried out continuously. However, the invention is also applicable to processes in which these two steps are discontinuous in a batch mode. Preferably, steam explosion is performed after cooking, but this explosion step is still optional.
Preferably, the impregnation in this embodiment can be carried out in a reactor with the biomass inlet located in a first impregnation zone of the impregnation reactor, said impregnation reactor comprising two superposed zones, namely said first impregnation zone and a second "draining" zone above the impregnation zone and equipped with an outlet for impregnated and drained biomass. More preferably, in this reactor configuration, liquid is introduced into the reactor via the first liquid inlet of the reactor located in the first impregnation zone of the reactor.
Thus, the invention in this example proposes recycling or reusing all or a portion of the washing fluid of both feed screws. A particularly advantageous feature is that it proves possible to effectively recycle one and/or the other washing fluid, or both, without affecting in any way the quality of the impregnation or the quality of the cooking.
Furthermore, this recirculation can be performed very flexibly in various ways for each washing fluid.
Thus, the washing fluid of the feed device of the impregnation reactor is generally water-based, so that "waste" water is mainly recovered at the outlet of the feed device. Recycling the waste water by reintroducing it into the inlet of one or the other of the screw-type feeding devices can significantly reduce the water consumption in the process. In addition, when heating the water, since the washing water as a whole requires less heat, energy saving is also observed. The circulation of the washing fluid in the closed loop is therefore very advantageous.
With regard to the washing fluid of the feeding device of the digestion pre-treatment reactor, the situation is slightly different, since the washing fluid (usually also water) tends to become catalyst-containing when washing the feeding device transporting the biomass that has been impregnated with catalytic liquid: in this screw a part of the liquid is pressed out of the impregnated biomass containing the catalyst and this liquid is mixed with the washing water therein at the outlet of the screw. At the outlet of the feeding device, it is usually called "press liquor". The press liquor may also be recycled to return to the wash inlet of the feed means of the pretreatment reactor, or to the wash inlet of the first feed means. Furthermore, even when the impregnation liquid is very acidic, and when the pressing liquid is also so (its degree of acidity is low), this does not pose any problem for the plant, since the biomass feed equipment of the impregnation reactor is typically designed to withstand contact with the catalytic liquid (to counter flooding of the liquid into the biomass feed equipment) without degradation.
In both cases, it is still possible to send a part of the waste water and/or the press liquor to the discharge as well. In addition, the two cases are either alternative or additive.
According to a preferred embodiment, the process of the present invention further comprises reintroducing a portion of the first washing fluid and/or the second washing fluid leaving the fluid outlet of the first feeding device or the second feeding device into the impregnation liquid preparation zone for a.) preparing said liquid.
During the process, the proportion of exiting washing fluid reintroduced into the feeding device with respect to the fluid used for the preparation of the catalytic liquid or with respect to the fluid delivered to the discharge can be adjusted and varied at will according to the needs.
In the case where a portion of the pressed liquid is reintroduced into the liquid preparation zone, the advantages are twofold, since the consumption of water for the preparation of the liquid is reduced, and the consumption of catalyst is reduced, since the pressed liquid contains the catalyst. The liquid preparation step is usually carried out with different adjustment means for certain physicochemical parameters (e.g. temperature), the content of catalyst in the liquid (e.g. by adjusting the pH value when acidic or basic catalysis is required), and therefore this additional catalyst supply can be taken into account by these adjustment means in order to maintain the desired properties of the liquid.
The washing of the first feeding device and/or the second feeding device can take place continuously or discontinuously, so that, for example, washing can take place permanently or at given time intervals. The wash circulation flow rate can also be varied, in particular as a function of the biomass mass flow rate introduced into one or the other reactor.
The reintroduction of a portion of the first washing fluid and/or the second washing fluid exiting the fluid outlet of the first feeding device or the second feeding device into the washing inlet of the first feeding device and/or the second feeding device may also occur continuously or discontinuously.
According to one embodiment, a portion of the first washing fluid at the washing outlet of the first feeding means is reintroduced into the washing inlet of the first feeding means or the second feeding means and another portion of said washing fluid is reintroduced into the liquid preparation zone for preparing said liquid.
Correspondingly, according to a second embodiment compatible with the previous embodiments, a portion of the second washing fluid at the washing outlet of the second feeding means is reintroduced into the washing inlet of the first feeding means or of the second feeding means, and another portion of said washing fluid is reintroduced into the liquid preparation zone for preparing said liquid.
According to one embodiment, the washing of the feeding device is carried out in the presence of biomass supplemented with a catalyst, in particular an acidic catalyst, a basic catalyst or an oxidative catalyst, the washing fluid leaving the fluid outlet of said feeding device contains a certain amount of said catalyst when the biomass is subjected to liquid extraction by passing through said feeding device, and at least a portion of said washing fluid containing said catalyst is reintroduced into the washing inlet of the same feeding device or of the other of said feeding devices, in particular conveying biomass free of catalyst. The term "catalyst" is to be understood herein in a broad sense as any agent capable of interacting with biomass, in particular for modifying one of its physicochemical or rheological properties. Thus, it was found by the present invention that the wash water (even when supplemented with such a catalyst) can be recycled to be reintroduced into the same feed device or another feed device which only delivers biomass: the fact that the reintroduced washing water is not pure water, but water supplemented with catalyst proves to have no detrimental effect on the overall process, which is unexpected.
Another subject of the present invention is an apparatus for carrying out the above process, in particular an apparatus comprising at least one reactor for treating lignocellulosic biomass having a solids content of not more than 90% by weight, wherein the biomass is fed to the reactor or at least one of the reactors by means of a feeding device generating a pressure increase between a biomass inlet and a biomass outlet of the feeding device. The feed device is washed by means of circulation of a washing fluid between a washing inlet and a washing outlet and reintroducing at least a portion of the washing fluid exiting the fluid outlet of at least one of the feed device or the feed device into the washing inlet of the other of the feed device or the same feed device.
Another subject of the invention is an embodiment of a lignocellulosic biomass processing plant comprising:
-a zone equipped with a liquid outlet for preparing an impregnation liquid comprising a chemical catalyst for impregnation of the biomass, said chemical catalyst being selected from an acid catalyst, a basic catalyst or an oxidation catalyst, preferably an acid catalyst;
a steeping reactor, in particular comprising a first steeping zone provided with a biomass inlet and a second steeping zone, called draining zone, superimposed on the first steeping zone, said reactor being provided with a biomass inlet and a biomass outlet;
-a first device feeding ground biomass to the impregnation reactor via a biomass inlet of the impregnation reactor, in particular located in the first impregnation zone;
-means for feeding the impregnation liquid to the reactor, which means connect the liquid outlet of the liquid preparation zone to the first liquid inlet in the impregnation reactor, in particular in the first impregnation zone of the impregnation reactor;
-a reactor for pretreating impregnated biomass by steam explosion, the biomass inlet of the reactor being connected to the biomass outlet of the impregnation reactor;
-a second device feeding impregnated biomass into the pretreatment reactor via the biomass inlet of the pretreatment reactor;
-circulation of a washing fluid between the inlet and the outlet of the first feeding device of the ground biomass of the impregnation reactor;
-circulation of a washing fluid between the inlet and the outlet of the second feeding device of the impregnated biomass of the pretreatment reactor;
the device further comprises:
-means for reintroducing at least a portion of the first and/or second washing fluid leaving the fluid outlet of the first or second feeding means into the washing inlet of the first and/or second feeding means.
Advantageously, the apparatus further comprises means for reintroducing a portion of the first washing fluid and/or the second washing fluid leaving the fluid outlet of the first feeding means or the second feeding means into the impregnation liquid preparation zone.
Advantageously, means for reintroducing a portion of the first washing fluid at the washing outlet of the first feeding means into the washing inlet of the first feeding means or of the second feeding means, and means for reintroducing another portion of said fluid into the liquid preparation zone can be envisaged.
The apparatus according to the invention can also envisage means for reintroducing a portion of the second washing fluid at the washing outlet of the second feeding means into the washing inlet of the first feeding means or of the second feeding means, and means for reintroducing another portion of said fluid into the liquid preparation zone.
These reintroduction devices are advantageously lines or groups of lines capable of making the desired hydraulic connections, the production of which is known per se.
Another subject of the present invention is the use of the above described method or apparatus for the treatment of any lignocellulosic biomass, such as wood, straw, agricultural residues and all dedicated energy crops, which may be annual or perennial plants, such as miscanthus, to produce sugars, biofuels or bio-based molecules.
Detailed Description
The invention will be described in detail below by means of non-limiting examples of the method according to the invention, which are illustrated by the following figures:
FIG. 1: a schematic diagram of the type of block diagram of the general principle of the biomass processing method according to the invention,
-figure 2: a schematic diagram of a block diagram type of a first embodiment of a biomass processing method according to the invention,
-figure 3: a schematic diagram of a block diagram type of a second embodiment of the biomass treatment process according to the invention,
-figure 4: schematic representation of a block diagram type of a third embodiment of a biomass processing method according to the invention.
Thus, fig. 1 is a schematic representation of the principles of the present invention, and fig. 2 focuses on two biomass processing steps: catalytic impregnation followed by cooking. Fig. 3 and 4 depict the entire process of treating biomass after impregnation and cooking until its enzymatic hydrolysis.
The invention focuses more specifically on the first two steps, namely impregnation of the ground biomass and treatment of the biomass by cooking once it has been impregnated.
The figures are described using the following reference numerals
Throughout the drawings, the same reference numbers correspond to the same components/fluids/products:
1: the water enters the liquid preparation tank
2: the acid enters a liquid preparation tank
3: liquid preparation equipment (tank)
4: acidic liquid entering impregnation equipment (reactor)
5: ground biomass
6: screw-type or plug-screw (plug-screw) feeder for impregnation plants
7: water for washing a screw feeder of an impregnation plant
8: washing liquid outlet of screw plug type feeder of impregnating equipment
9,9': impregnation apparatus (reactor)
9 a: impregnation zone of the impregnation tank 9
9 b: draining zone of impregnation tank 9
10: impregnated and drained biomass
11: screw feeder or plug screw feeder for pretreatment equipment
12: water for washing a screw-type feeder of a pretreatment device
13: squeezing liquid of screw plug type feeder of pretreatment equipment
13, a: sending the squeezed liquid to discharge
13, b: plug screw feeder for recycling press liquor to wash pretreatment equipment
13, c: recycling the pressed liquid to the acidic liquid preparation tank 3
13, d: plug screw feeder for recycling press liquor to wash impregnation equipment
14: pretreatment cooking equipment (blasting reactor)
15: steam injection for pretreatment
16: pretreated biomass and steam
17: device for separating steam and pretreated biomass (cyclone)
18: condensation of steam
19: pretreated biomass
20: enzymatic hydrolysis
21: sugar-containing enzymatic hydrolysates
22: alcohol (ethanol) fermentation
23: fermented wine containing ethanol
24: distillation
25: concentrated alcohol
26: crude distiller's grains.
Fig. 1 shows the principle of the invention in a very schematic way in its simplest embodiment (the details of its process and the individual steps will be described later with the aid of fig. 2 to 4): the
According to the invention, at least a part of the washing water leaving the
In this illustration, the recirculation of the washing water is applied to the same spiral, but, as will be described in detail in the other figures, when the process envisages a plurality of feeding spirals for a plurality of reactors, the invention also relates to the recirculation, in whole or in part, of the washing water at the outlet of one spiral to the inlet of another feeding spiral.
Here, the solids content of the biomass entering the feed screw is 50%. It may happen that during the transport of the biomass in the spiral a part of the liquid is extracted, the extracted water being mixed with the spent washing water at the washing outlet of the spiral. The lower the solids content of the biomass, the more fluid is extracted from the biomass in the feed screw, which fluid supplements or even optionally replaces the washing fluid at the inlet of the screw completely.
Figure 2 shows the step of impregnating the biomass with an acidic liquid, followed by a cooking step which forms part of the biomass treatment:
the method is carried out in the following manner: water and acid are introduced into the acidic liquid preparation tank 3 via line 1 and
The impregnated biomass 10, which has optionally been drained beforehand, is introduced into the
Optionally, a solid/liquid separation step is carried out on this
-discharge via line 13 a;
recirculation via line 13b to replace all or part of the
recycled to the acidic liquid preparation tank 3 via line 13 c.
Then various possibilities become available:
according to one embodiment,
according to another embodiment, only a portion of
The biomass is treated in the
Fig. 3 illustrates a variant with respect to fig. 2 in carrying out the impregnation of the biomass and also illustrates the steps following the cooking/steam explosion of the biomass.
Only the differences from the method according to fig. 2 are described here, in other respects both methods are carried out in the same way.
Water and acid are introduced into the acidic liquid preparation tank 3 via line 1 and
The pre-ground biomass is introduced into the process via
-discharge via line 13 a;
recirculation via line 13b to replace all or part of the
via line 13c to the acidic liquid preparation tank 3;
but another possibility can be used, since here too the
Continuing with the
the steam required for heating the
The pretreated biomass is then converted in a
Details of the operating conditions for the steam explosion, enzymatic hydrolysate conversion and fermentation steps which are considered to be known to the person skilled in the art will not be given herein.
Fig. 4 shows a variant with respect to fig. 3.
Other reference numbers relative to fig. 3 are:
8: waste washing liquid outlet of spiral 6 of impregnating equipment
8, a: waste washing liquid sent to discharge
8, b: recirculating washer fluid cyclone for washing immersion apparatus screws
8, c: the washing liquid recycled to the acidic liquid preparation tank 3
8, d: recycled washing liquid for washing the screw 11 of the
Only the differences from the method according to fig. 3 are described here, in other respects the two methods proceed in the same way:
here, the water 8 washing the feed screw 6 is also recirculated according to various alternative or superposition possibilities. The liquid 8 used for washing the conveyor screw 6 may be:
discharge from the system via line 8a
Water 7 recycled via line 8b to replace the feed screw 6 of the washing impregnation reactor 9
Recycled to the acidic liquid tank 3 via line 8c, or
According to another embodiment of the invention, stream 8 is sent in its entirety to line 8b or to line 8d, replacing all or part of the
In any case, with the recirculation of the waste water coming from the screw 6 or of the pressing liquid coming from the screw 11, a portion can also be sent to discharge (line 13a, line 8 a).
It goes without saying that in the context of the present invention, it is also possible to combine the recirculation of the waste water from the washing screw 6 with the recirculation of the pressing liquid from the screw 11, or to recirculate only one of them.
Some operational details or variations on the first two biomass treatment steps described above are given below:
the impregnation step is carried out at a temperature of 10-95 ℃ and the residence time of the biomass in the impregnation step is 20 seconds to 12 hours. Preferably, the residence time of the biomass is from 30 seconds to 60 minutes.
The impregnation step may be carried out in a batch or continuous mode. Preferably, this step is carried out in a continuous mode. The impregnation step is preferably carried out at atmospheric pressure. Preferably, the impregnation step is performed in a single step.
The impregnation step comprises contacting the biomass with an acidic liquid. It can be carried out, for example, by dipping or by spraying.
The impregnation step is carried out in apparatuses known to the person skilled in the art, for example in stirred reactors, by horizontal or vertical passage of the biomass in a liquid bed, by spraying on a conveyor belt conveying the biomass (as shown in fig. 2) or in a conveying screw.
Impregnation reactors or impregnators are generally equipped with one or more devices for transferring the lignocellulosic substrate from its inlet orifice to its outlet orifice. These devices may be, for example, screws or conveyor belts. Furthermore, the impregnator is equipped with one or more lines for conveying the acidic liquid and, if desired, with one or more lines for withdrawing the acidic liquid. The inlet and outlet pipes for the acidic liquid are typically installed to function by co-current or counter-current recirculation.
Pretreatment step (cooking):
this pre-treatment step is carried out on the lignocellulose substrate, which is specifically intended to modify the physical and physicochemical properties of the cellulose fraction, such as its degree of polymerization and its crystalline state.
The pretreatment includes a cooking zone. The cooking is carried out at a temperature of from 100 ℃ to 250 ℃, more preferably from 130 ℃ to 230 ℃, at a pressure of from 0.1 to 4 MPa. The residence time in the cooking zone is from 10 seconds to 4 hours, more preferably from 3 minutes to 1 hour.
Cooking may be carried out in batch or continuous mode. It can be carried out in any apparatus known to the person skilled in the art, such as stirred reactors, horizontal tubular reactors equipped with a conveyor screw, unstirred batch reactors, etc. The thermal energy required for cooking can be provided by heat exchange (indirectly) with a heat transfer fluid, by electrical heating or by direct injection of a hot fluid, such as pressurized water or steam.
The discharge of solids at the end of cooking can take place by rapid depressurization, slow depressurization, after a temperature drop by direct or indirect heat exchange, etc.
In one embodiment (preferred), the cooking zone is heated with steam by direct injection, and then the medium is subjected to sudden decompression, a process known as steam explosion (or "steamex"). In this process, the lignocellulosic substrate is brought rapidly to high temperature by injection of pressurized steam. The treatment was stopped by sudden decompression.
The operating conditions of the steam explosion process were as follows:
injecting steam directly into the reactor;
the temperature of the reactor is generally 150 ℃ and 250 ℃, preferably 160 ℃ to 220 ℃;
a pressure of 0.5-2.5 MPa, preferably 0.8-2.0 MPa;
the residence time before the expansion stage is from 10 seconds to 25 minutes, preferably from 3 minutes to 15 minutes.
The steam explosion may be performed in a batch or continuous mode, and the depressurization step to achieve destruction of the biomass structure may be performed in one or more steps.
An embodiment using the method according to fig. 4 to implement one or more recycling operations is now described:
comparative example 1
This is an embodiment in which only the waste washing water is recycled as make-up water for the liquid preparation tank. The biomass to be treated is wood having the following characteristics:
raw materials: poplar, flow 7.47 ton/hr, Solid Content (SC): 50%, average composition (based on SC):
% (based on SC)
Cellulose, process for producing the same, and process for producing the same
42.6%
Hemicellulose
20.5%
Lignin and others (ash, extractables, etc.)
36.9%
The acronym "SC" denotes Solids content, which is determined according to the standard ASTM E1756-08(2015), "Standard Method for Determination of Total Solids in Biomass".
The wood is used in the form of chips with a characteristic size of 50 mm. The temperature of the debris entering the cell is room temperature. The
The following are introduced into the impregnation reactor 9:
-wood chips compressed via a conical screw 6;
an
The impregnated chips are removed from the impregnation reactor 9 and transferred to the
The steam explosion pretreatment was carried out in a continuous configuration with a short residence time at 200 ℃. The medium suddenly expands to a pressure of 1.3 atmospheres.
The acidic liquid preparation tank 3 located upstream of the impregnation delivers a flow of acidic liquid of 2.9 tonnes/hour. The liquid was prepared from water and 96% sulfuric acid, each at a flow rate of 2.8526 tons/hour water and 0.0474 tons/hour acid at a concentration of 96% by weight. In this configuration, the total water consumption was 4.5526 tons/hour, the total acid consumption was 0.0474 tons/hour of sulfuric acid having a concentration of 96 wt.%.
Waste water from washing screw 6 and screw 11 is discharged via line 8a and line 13 a.
Comparative example 2
This example repeats comparative example 1, the only difference being that a portion 13c of the stream resulting from washing the spiral 11 of the blasting
Example 3 according to the invention
In this example, a method of impregnating and pretreating wood according to the present invention is presented, which treats the same raw materials as in the aforementioned comparative examples 1 and 2. The wood is used in the form of chips with a characteristic size of 50 mm. The temperature of the debris entering the cell is room temperature.
The chips are transported via a conical screw 6 to an impregnation reactor 9. The helix was washed with washing solution 7, 8, 13d at a flow rate of 1.0 ton/hour; the liquid is generated from a mixture of water 7 and liquid 13d used to wash the spiral 11 of the
The following are introduced into the impregnation reactor 9:
-compressed wood chips via the conical spiral 6;
2.9 tons/hour of
The impregnated chips are removed from the impregnation reactor 9 and transferred to the
The acidic liquid preparation tank 3 located upstream of the impregnation delivers a flow of acidic liquid of 2.9 tonnes/hour. Preferably, it is equipped with sensors for measuring pH and flow of water, acids, waste and process liquids.
A part of the stream resulting from washing the spiral 11 of the blasting
Thus, with respect to the configuration of comparative example 2, the method according to the invention can achieve:
the mass consumption of water is reduced by more than 42%;
a 29% reduction in the mass of the wastewater to be treated.
Example 4 according to the invention
In this example, a method of impregnating and pretreating wood according to the present invention is presented, which treats the same raw materials as in comparative example 1.
The wood is used in the form of chips with a characteristic size of 50 mm. The temperature of the debris entering the cell is room temperature.
The chips are transported via a conical screw 6 to an impregnation reactor 9. The helix was washed with wash water 7 at a rate of 1.0 tonne/hour. In the compression carried out by means of a screw, liquid was extracted from the poplar chips at a rate of 0.679 tonnes/hour, so that the total flow of waste water used for washing the screw 6 of the impregnation reactor 9 was 1.679 tonnes/hour.
The following are introduced into the impregnation reactor 9:
-compressed wood chips via a
2.9 tons/hour of
The impregnated chips are removed from the impregnation reactor 9 and transferred to the
The acidic liquid preparation tank 3 located upstream of the impregnation delivers a flow of acidic liquid of 2.9 tonnes/hour.
In the method according to this example, the total water consumption is 1.0 ton/h (for washing the impregnation screw 6) and the acid consumption is 96 wt% sulfuric acid of 0.0294 ton/h. A waste water stream of 1.759 tonnes/hour must be treated.
Thus, with respect to the configuration of comparative example 2, the method according to this embodiment of the present invention can realize:
the mass consumption of water is reduced by 37%;
the mass consumption of concentrated sulfuric acid is reduced by 9.4 percent
A 25% reduction in the mass of the wastewater to be treated.
In summary, these examples show that the invention provides a very significant saving in energy/starting material and great flexibility of implementation. Moreover, the modifications made to the device are still modest and easy to implement, adding, where appropriate, lines equipped with devices for varying the flow, measuring the pH or the temperature, the idea of these additional lines being entirely within the reach of the person skilled in the art. Even if the various operations for treating the biomass (such as impregnation and cooking and/or steam explosion operations) are not continuous, the present invention is still beneficial: in this case, it is preferred to recycle the wash water to the same feed screw (loop 8b for the washing of screw 6, loop 13b for the washing of screw 11).
- 上一篇:一种医用注射器针头装配设备
- 下一篇:用于聚酯类材料的浓缩物