Patent Application
20180016607
The present invention relates to methods for process control. In particular the invention relates to control of processes of pretreatment of a soft wood biomass to improve the digestibility of the biomass.
Biorefineries producing green chemicals and fuels from renewable resources offer an alternative to oil refineries based on dwindling supplies of petroleum and permit a move towards improved energy security. Lignocellulosic residues from forestry are attractive as feedstocks, since they are abundant, relatively inexpensive, and are not used for food. Lignocellulose consists mainly of lignin and two classes of polysaccharides, cellulose and hemicellulose. The polysaccharides can be hydrolyzed to sugars which can be used as a platform chemical for the production of a host of other chemicals, for example by fermentation of the sugars in to various fermentation products, such as bioalcohols. The fermentation processes utilizes fermenting agents to convert the sugar in to fermentation products. One such fermenting agent is baker's yeast (Saccharomyces cerevisiae) which can be used to ferment sugars in to ethanol. The hydrolysis of cellulose is typically preceded by a pretreatment, in which the cellulose is made more digestibility, such as more accessible to cellulolytic enzymes.
To render the cellulose more accessible for the enzymes in a subsequent enzymatic hydrolysis step, it is important that the pretreatment is severe enough. However, too harsh pretreatment leads to degradation of sugars and increased levels of substances which are toxic to the hydrolytic enzymes and to fermenting organisms. Examples of such toxic substances include furfural, hydroxymethylfurfural, acetic acids and phenolic compounds. An accurately controlled pretreatment step is therefore important for the yield in subsequent process steps, such as for example enzymatic hydrolysis and fermentation.
The present inventor has surprisingly discovered that a calculated ratio between glucose and mannose in a slurry of pretreated soft wood can be used to determine if the pretreatment process has been too harsh or to mild. Based on this discovery the inventor has further realized that a process of pretreating softwood can be controlled by measuring the ratio glucose:mannose, comparing the ratio to a reference value and controlling at least one process parameter of the pretreatment process in response to a difference between the measured ratio and the reference value.
Thus, a first aspect of the present invention relates to a method for pretreating a softwood starting material comprising the following steps:
a) pretreating the softwood starting material in a pretreatment process to form a slurry;
b) measuring the concentration of glucose and the concentration of mannose in the slurry formed in step a);
c) calculating a ratio glucose:mannose from the concentrations measured in step b)
d) comparing the ratio calculated in step c) to a reference value and if the ratio calculated in step c) differs from the reference value, controlling at least one process parameter of the pretreatment process in response to the difference.
An effective pretreatment is needed to liberate the cellulose in a lignocellulosic starting material from the lignin seal and its crystalline structure so as to render it accessible for a subsequent hydrolysis step. If the pretreatment is not harsh enough, it will be harder to hydrolyze the carbohydrates to sugars, and/or to digest it to biogas. However, if the pretreatment is too harsh, larger amounts of sugars will be degraded and fermentation inhibitors such as HMF, furan aldehydes (e.g. furfural), acetic acid and/or phenolic compounds will be formed, which in turn might impair hydrolysis and/or fermentation processes. Similarly, a too harsh pretreatment can also reduce the yield from a biogas digestion process. Efficient control of the pretreatment step is thus highly beneficial for processes for production of green chemicals from lignocellulosic biomass. The composition of a slurry of pretreated lignocellulosic biomass will differ depending on the severity of the pretreatment. For example the concentration of inhibitors and sugars will change in response to the severity of the pretreatment. The present inventor has realized the concentration of different specific molecules in the pretreated slurry can be monitored in order to measure the harshness of the pretreatment. Surprisingly, the present inventor has demonstrated that, if the biomass is a softwood biomass, the ratio between glucose and mannose can be used to determine if the pretreatment process has been too harsh or to mild. The inventor has further demonstrated that the pretreatment process can be controlled by comparing the ratio to a reference value. If the ratio differs from the reference value, the pretreatment process can be controlled by adjusting at least one process parameter of the pretreatment process in response to the difference.
Given the fact that the concentration of a host of different molecules will change during the pretreatment step, and vary in concentration depending on the severity of the pretreatment step, it is highly surprising that the pretreatment step can be efficiently controlled simply by measuring the concentration of two specific molecules, i.e. glucose and mannose. Importantly, the present inventor has demonstrated that this method is suitable for some lignocellulosic substrates but not for other. In particular, the method works very well for controlling the pretreatment of a softwood starting material but does not appear to be suitable for controlling the pretreatment of straw.
Thus, a first aspect of the present invention relates to a method for pretreating a softwood starting material comprising the following steps:
a) pretreating the softwood starting material in a pretreatment process to form a slurry;
b) measuring the concentration of glucose and the concentration of mannose in the slurry formed in step a);
c) calculating a ratio glucose:mannose from the concentrations measured in step b)
d) comparing the ratio calculated in step c) to a reference value and if the ratio calculated in step c) differs from the reference value, controlling at least one process parameter of the pretreatment process in response to the difference.
An accurate pretreatment is important for subsequent step such as production of green chemicals from the slurry. Production of such green chemicals can involve hydrolyzing the cellulose present in the slurry into sugars. Thus in one embodiment the method further comprise the step
e1) hydrolyzing the slurry obtained in step a) such that a sugar solution is obtained. In a preferred embodiment the hydrolyzing in step e1) is enzymatic hydrolysis. The sugars obtained from the hydrolysis process can for example be fermented in to a target chemical. Thus, in one embodiment the method further comprising the step
f) fermenting the sugar solution obtained in step e1) using an fermenting agent such that a fermentation product is obtained. In one embodiment step e1) and step f) is performed simultaneously in an simultaneous saccharification and fermentation process (SSF). In another embodiment step e1) and step f) is performed separately in a separate hydrolysis and fermentation process (SHF). In one embodiment at least one endoglucanase, at least one exoglucanase and at least one β-glucosidase is added in step e1). In one embodiment the fermentation product is selected from alcohols, acids, alkanes, alkenes, aromatics, aldehydes, ketones, biopolymers, proteins, peptides, amino acids or vitamins. In a preferred embodiment the fermentation product is selected from ethanol, butanol, acetic acid, butyric acid and succinic acid. In one embodiment the fermenting agent is bacteria and/or yeast. In one embodiment the fermenting organism is yeasts from the genera Saccharomyces, Pichia or Candida. In one embodiment the fermenting organism is wild type, mutant or recombinant Saccharomyces cerevisiae. In another embodiment the fermenting organism is bacteria from the genera Zymomonas or Escherichia.
The pretreated slurry can also be used for anaerobic digestion of the slurry into biogas. The requirements of a pretreated slurry which shall be used as a substrate for biogas digestion is similar to the requirements of a pretreated slurry which shall be used for production of sugars by a hydrolytic process, such as an enzymatic hydrolysis process. Thus in one embodiment the method further comprising the step
e2) anaerobic digestion of the slurry obtained in step a) or of the sugar solution obtained in step e1) such that biogas is obtained.
The present inventor has discovered that a mild pretreatment gives rise to a lower glucose:mannose ratio than a more severe pretreatment. Furthermore, the inventor has discovered that if the starting biomass is softwood, it is possible to control the pretreatment process by analyzing the ratio in the pretreated slurry and comparing it to a reference value. If the value is lower than the reference value, process parameters can be adapted such that the severity of the pretreatment is increased. Conversely, If the ratio glucose:mannose is higher than the reference value, this is an indication of that the pretreatment has been too severe. Thus, the pretreatment can be controlled by adjusting process parameters such that the severity of the pretreatment is decreased.
Therefore, In one embodiment;
The present inventor has discovered that a ratio (w/w) of glucose:mannose in the pretreated slurry in the range 1:1 to 1.6:1 gives rise to a high yield of product produced in subsequent step. For example a high yield of sugars can be produced in a subsequent enzymatic hydrolysis step and a high yield of ethanol fermented from the sugars produced in the enzymatic hydrolysis step. The inventor has discovered that lower yields of fermentation product is obtained if the ratio (w/w) of glucose:mannose in the pretreated slurry fall outside of this defined range. Therefore, in one embodiment the ratio (w/w) glucose:mannose is calculated in step c) and the reference value is in the range 1:1 to 1.6:1 preferably 1.1:1 to 1.5:1.
As can be seen from
In one embodiment the reference value is an interval. In one embodiment the interval is 1:1 to 1.6:1 preferably 1.1:1 to 1.5:1 most preferably 1.2:1 to 1.4:1.
There are several advantages with using the glucose:mannose ratio for controlling the severity of the pretreatment of a soft wood biomass. First of all, the method is solid and by controlling the pretreatment, such that the ratio is kept within a predetermined interval, a high yield of product can be obtained. The present inventor has not found any other chemicals in the pretreated slurry which is as useful for controlling the pretreatment process or for predicting the yield from subsequent enzymatic hydrolysis or fermentation steps. Furthermore, the measurement of glucose and mannose is simple and accurate compared to several other chemicals. For example the concentration of HMF is harder to measure accurately and does not predict the obtained yield from subsequent enzymatic hydrolysis or fermentation steps as good as the glucose:mannose ratio, data not shown.
In the context of the present disclosure, “pretreating” refers to modifying a lignocellulosic starting material to make the cellulose therein more accessible to hydrolytic activity in a subsequent hydrolysis step. However, in some embodiments of the present disclosure, the pretreatment can be performed to make the lignocellulosic starting material more suitable to anaerobic digestion for the production of biogas. The person of skill in the art is well aware of various pretreatment methods that may be employed for that purpose. As an example, the pretreatment may be acidic pretreatment or alkali pretreatment. Thus, the pretreatment may be aided by the addition of a catalyst. The catalyst may be added as a fluid in an impregnation step, which is followed by a heating step. The heating is normally achieved by the addition of steam. The fluid may be an acidic solution, such as an aqueous mineral acid solution, such as sulfuric or sulfurous acid. The impregnation may also be performed with a gas, such as a SO2 gas or CO2 gas, or with the combination of a gas and a liquid. The pretreatment may also comprise steaming. Steaming refers to a process used to drive air out from the cellulosic biomass to facilitate further hydrolysis of the cellulose. Steaming is a well-known method for pretreating e.g. lignocellulosic biomass. As another example, the pretreatment may involve steam explosion. Steam explosion is a process that combines steam, rapid pressure release and hydrolysis for rupturing cellulosic fibers. Steam explosion may be performed with or without a preceding addition of a catalyst. Thus, in one embodiment the pretreatment is acidic pretreatment using an acidic catalyst or alkaline pretreatment using an alkaline catalyst. In one preferred embodiment the pretreatment is acidic pretreatment using an acidic catalyst. In one embodiment the acidic catalyst is an acid solution, such as a mineral acid solution or a gas such as a sulfur dioxide. In one embodiment the catalyst is selected from sulfuric acid, sulfurous acid and sulfuric acid. In one embodiment the pretreatment includes steam explosion. In one embodiment the pretreatment is a dilute acid pretreatment.
The most important severity parameters of the pretreatment process reaction is the pH, the temperature, the pressure and the residence time of the starting material in the pretreatment process. Therefore, in one embodiment the process parameter of the pretreatment process is controlled by:
In one embodiment process parameter of the pretreatment process is controlled such that the severity of the pretreatment is increased by:
In one embodiment process parameter of the pretreatment process is controlled such that the severity of the pretreatment is decreased by:
In one embodiment the temperature of the pretreatment in step a) is 190-225° C., such as 200-220° C.
In one embodiment the pH of the pretreatment in step a) is 1.2-2.2, preferably 1.2-2.0. In one embodiment the residence time in the pretreatment step is 3-10 min, such as 4-8 minutes.
The concentration of glucose and mannose can be measured using any method known in the art. HPLC based technique can for example be used in the process of measuring glucose and mannose concentration.
In one embodiment the softwood starting material is shaving or chips from softwood. In one embodiment the softwood starting material comprises spruce, pine and/or fir.
Wood chips from spruce was pretreated at several different conditions using temperatures ranging between 200-220° C.; pH in the range 1.2-2.0 and residence times in the range 4-8 minutes in a continuous vertical pretreatment reactor followed by steam explosion. The HMF concentrations, the glucose concentrations and the mannoses concentration in the obtained pretreated slurries were measured using HPLC based methods. The pretreated slurries were thereafter subjected to enzymatic hydrolysis for 24 h using commercially available preparations of cellulase and cellobiase. The glucose concentrations in the obtained hydrolysates were thereafter measured using HPLC based methods. The weight ratios of glucose to mannose in the pretreated slurries were calculated. In
| Number | Date | Country | Kind |
|---|---|---|---|
| 1550104-2 | Feb 2015 | SE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SE2016/050034 | 1/20/2016 | WO | 00 |
