METHOD FOR RETAINING A MUD CATALYST IN A DESIRED LOCATION

专利摘要:
method for retaining a mud catalyst in a desired location. Digesting cellulosic biomass in the presence of a sludge catalyst can reduce degradation product formation but catalyst distribution and retention can be problematic. Digestion methods may comprise: providing cellulosic biomass solids and a sludge catalyst capable of activating molecular hydrogen in a digestion unit; providing a digestible filter aid in the digestion unit; distributing the slurry catalyst into the cellulosic biomass solids using fluid flow; retaining at least a portion of the slurry catalyst in a fixed location using the digestible filter aid; heating cellulosic biomass solids in the presence of sludge catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; and performing a catalytic reduction reaction on soluble carbohydrates in the digestion unit, thereby at least partially forming a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof in the digestion unit.
公开号:BR112014032117B1
申请号:R112014032117-5
申请日:2013-06-27
公开日:2021-06-01
发明作者:Glenn Charles Komplin；Joseph Broun Powell
申请人:Shell Internationale Research Maatschappij B.V.；
IPC主号:

专利说明:

Field of Invention
[001] The present disclosure generally refers to digestion and, more specifically, to methods for retaining a sludge catalyst in a desired location while digesting cellulosic biomass solids. Fundamentals of the Invention
[002] Numerous substances of commercial significance can be produced from natural sources, including biomass. Cellulosic biomass can be particularly advantageous in this regard because of the versatility of the abundant carbohydrates found in it in various forms. As used herein, the term "cellulosic biomass" refers to a living or newly living biological material that contains cellulose. The lignocellulosic material found in the cell walls of higher plants is the world's most abundant source of carbohydrates. Materials commonly produced from cellulosic biomass can include, for example, paper and wood pulp through partial digestion and bioethanol through fermentation.
[003] Plant cell walls are divided into two sections: primary cell walls and secondary cell walls. The primary cell wall provides structural support for expanding cells and contains three main polysaccharides (cellulose, pectin and hemicellulose) and a group of glycoproteins. The secondary cell wall, which is produced after the cell has just grown, also contains polysaccharides and is reinforced by polymeric lignin which is covalently cross-linked to hemicellulose.
[004] Hemicellulose and pectin are typically found in abundance, but cellulose is the predominant polysaccharide and the most abundant carbohydrate source. The complex mixture of constituents that are co-present with the cellulose can make its processing difficult, as discussed below.
[005] Significant attention has been paid to the development of fossil fuel alternatives derived from renewable resources. Cellulosic biomass has gained particular attention in this regard because of its abundance and the versatility of the various constituents found in it, particularly cellulose and other carbohydrates. Despite promise and intense interest, development and implementation of biofuel technology has been slow. Existing technologies have hitherto produced fuels that have a low energy density (eg bioethanol) and/or that are not fully compatible with existing engine designs and transport infrastructure (eg methanol, biodiesel, Fischer-Tropsch diesel, hydrogen and methane). An energy and cost effective process for processing cellulosic biomass into fuel blends with compositions similar to fossil fuels would be highly desirable to address the above and other problems.
[006] During the conversion of cellulosic biomass into fuel mixtures and other materials, cellulose and other complex carbohydrates in them can be extracted and transformed into simpler organic molecules, which can be further reformed below. Fermentation is a process whereby complex carbohydrates from biomass can be converted into a more usable form. However, fermentation processes are typically slow, require large volume reactors, and produce an initial reaction product with a low energy density (ethanol). Digestion is another way in which cellulose and other complex carbohydrates can be converted into a more usable form. Digestion processes can break down cellulose and other complex carbohydrates in cellulosic biomass into simpler soluble carbohydrates that are suitable for further transformation through downstream reforming reactions. As used herein, the term "soluble carbohydrates" refers to monosaccharides or polysaccharides that become solubilized in a process of digestion. It is understood that, although the underlying chemistry is behind digestion of cellulose and other complex carbohydrates and additionally transformation of simple carbohydrates into organic compounds reminiscent of those present in fossil fuels, high-yield and energy-efficient digestion processes suitable for converting Cellulosic biomass in fuel blends have yet to be developed. In this regard, the most basic requirements associated with converting cellulosic biomass to fuel blends using digestion and other processes are that the energy input required to drive the conversion must not be greater than the energy output from the fuel product blends. This basic requirement leads to numerous secondary problems that collectively present a huge engineering challenge that has not been solved before.
[007] The problems associated with converting cellulosic biomass into fuel blends in a cost and energy-effective manner using digestion are not only complex, but they are totally different from those found in digestion processes commonly used in the paper and paper industry. wood pulp. Since the intention of cellulosic biomass digestion in the paper and wood pulp industry is to retain a solid material (eg wood pulp), incomplete digestion is usually carried out at low temperatures (eg less than 100°C) for a very short period of time. In contrast, digestion processes suitable for converting cellulosic biomass into blends of fuel and other materials are ideally configured to maximize yields by solubilizing the original cellulosic biomass load as much as possible in a high-throughput manner.
[008] The production of larger amounts of soluble carbohydrates for use in blends of fuel and other materials through routine modification of paper and wood pulp digestion processes is not feasible for a number of reasons. Simply running the pulp and paper industry's digestion processes for a longer period of time to produce more soluble carbohydrates is undesirable from a production standpoint. Use of digestion enhancers such as strong alkalis, strong acids, or sulfites to accelerate the rate of digestion can increase process costs and complexity because of post-processing separation steps and the possible need to protect downstream components from these agents. Accelerating the rate of digestion by increasing the digestion temperature can actually reduce yields because of the thermal degradation of soluble carbohydrates that can occur at elevated digestion temperatures, particularly for extended periods of time. Once produced by digestion, soluble carbohydrates are very reactive and can quickly degrade to produce caramels and other heavy end degradation products, especially at higher temperature conditions such as above 150°C. Use of higher digestion temperatures may also be undesirable from an energy efficiency standpoint. Any of these difficulties can negate the economic viability of fuel blends derived from cellulosic biomass.
[009] One way in which soluble carbohydrates can be protected from thermal degradation is by subjecting them to one or more catalytic reduction reactions, which may include hydrogenation and/or hydrogenolysis reactions. Stabilizing soluble carbohydrates by conducting one or more catalytic reduction reactions can allow cellulosic biomass digestion to occur at higher temperatures, which would otherwise be possible without sacrificing too much yields. Reaction products comprising triols, diols, monohydric alcohols, and any combination of these can be produced as a result of carrying out one or more catalytic reduction reactions on soluble carbohydrates. These reaction products can be easily transformable into mixtures of fuel and other materials through downstream reforming reactions. Furthermore, the above reaction products are good solvents in which a hydrothermal digestion can be carried out. The use of such solvents, which may include monohydric alcohols, glycols, and ketones, for example, can accelerate digestion rates and aid in the stabilization of other components of cellulosic biomass, such as lignins, for example, which may otherwise agglomerate and soil process equipment. Solvent separation and recycling can sometimes require extensive amounts of energy input, which can reduce the net energy output available from fuel blends derived from cellulosic biomass. By using the reaction product as a solvent, the net energy output of the fuel mixtures can be increased because of less need for separation steps to take place.
[0010] Another problem associated with processing cellulosic biomass in blends of fuel and other materials is created by the need for high conversion percentages of a cellulosic biomass load into soluble carbohydrates. As cellulosic biomass solids are digested, their size gradually decreases to the point where they can become fluidly mobile. As used herein, cellulosic biomass solids that are fluidically mobile, particularly cellulosic biomass solids that are 3 mm or less in size, will be referred to as "cellulosic biomass fines." Unless retained in some way, such as by use From a screen, filter, or similar retention mechanism, cellulosic biomass fines can be fluidly transported from a digestion zone of the system and to one or more zones where solids are unwanted and can be detrimental. the potential to clog catalyst beds, transfer lines, and the like Even when using a screen, filter, or similar retention mechanism, cellulosic biomass fines can eventually become so small that they pass through their openings. , cellulosic biomass fines can represent a non-trivial fraction of the cellulosic biomass load and, if they are not digested and added, converted to a reaction product, the ability to obtain a satisfactory yield may be compromised. Since the digestion processes of the paper and wood pulp industry are run at relatively low cellulosic biomass conversion percentages, it is believed that smaller amounts of cellulosic biomass fines are generated and have a smaller impact on those digestion processes.
[0011] In addition to the desired carbohydrates, other substances may be present in cellulosic biomass that can be especially problematic to deal with in a cost and energy effective manner. Sulfur and/or nitrogen containing amino acids or other catalyst poisons may be present in cellulosic biomass. If not removed, these catalyst poisons can impact the catalytic reduction reaction(s) used to stabilize soluble carbohydrates, thereby resulting in process downtime for catalyst regeneration and/or replacement and reducing the overall energy efficiency when restarting the process. On the other hand, in-process removal of these catalyst poisons can also impact the energy efficiency of the biomass conversion process, since the ion exchange processes typically required to carry out their removal are typically conducted at temperatures below those at which soluble carbohydrates they are produced by digestion, thereby introducing heat exchange operations that increase design complexity and can increase operating costs. In addition to catalyst poisons, lignin, which is a non-cellulosic biopolymer, can get solubilized along with the production of soluble carbohydrates. If not addressed in some way, lignin concentrations can become sufficiently high during biomass conversion for precipitation to eventually occur, thereby resulting in costly system downtime. Alternatively, part of the lignin may remain unsolubilized, and costly system downtime may eventually be required to carry out its removal.
[0012] As evidenced by the above, the efficient conversion of cellulosic biomass into fuel blends is a complex problem that presents immense engineering challenges. The present disclosure addresses these challenges and provides related advantages as well. Invention Summary
[0013] The present disclosure generally relates to digestion and more specifically to methods for retaining a sludge catalyst in a desired location while digesting cellulosic biomass solids.
[0014] In some embodiments, the present disclosure provides methods comprising: providing cellulosic biomass solids and a slurry catalyst in a hydrothermal digestion unit, the slurry catalyst being capable of activating molecular hydrogen ("Hydrogen Activating Slurry Catalyst" Molecular"); providing a digestible filter aid in the hydrothermal digestion unit; distributing the slurry catalyst into the cellulosic biomass solids using fluid flow; retaining at least a portion of the slurry catalyst in a fixed location using the digestible filter aid; heating the cellulosic biomass solids in the hydrothermal digestion unit in the presence of sludge catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; and performing a first catalytic reduction reaction on soluble carbohydrates in the hydrothermal digestion unit, thereby at least partially forming a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof in the digestion unit hydrothermal.
[0015] In some embodiments, the present disclosure provides methods comprising: providing cellulosic biomass solids and a slurry catalyst in a hydrothermal digestion unit, the slurry catalyst being capable of activating molecular hydrogen ("Hydrogen Activating Slurry Catalyst" Molecular"), and cellulosic biomass solids comprising a digestible filter aid comprising cellulosic biomass particulates capable of forming a filter cake suitable for retaining at least a portion of the slurry catalyst therein; distribute the slurry catalyst into the cellulosic biomass solids using upward directed fluid flow; heating the cellulosic biomass solids in the hydrothermal digestion unit in the presence of sludge catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; allowing a portion of the liquor phase to exit the hydrothermal digestion unit; forming a filter cake comprising the digestible filter aid in a solids retention mechanism configured to let the liquor phase pass therethrough; collecting at least a portion of the slurry catalyst in the filter cake; and performing a first catalytic reduction reaction on soluble carbohydrates in the hydrothermal digestion unit, thereby at least partially forming a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof in the hydrothermal digestion unit .
[0016] The features and advantages of the present disclosure will be readily apparent to those skilled in the art upon reading the description of the modalities that follow. Detailed Description of the Invention
[0017] The present disclosure generally relates to digestion and more specifically to methods for retaining a sludge catalyst in a desired location while digesting cellulosic biomass solids.
[0018] In the modalities described here, the digestion rate of cellulosic biomass solids can be accelerated in the presence of a digestion solvent. In some cases, the digestion solvent can be maintained at elevated pressures that keep the digestion solvent in a liquid state above its normal boiling point. Although the faster digestion rate of cellulosic biomass solids under these types of conditions may be desirable from a production standpoint, soluble carbohydrates may be susceptible to degradation at elevated temperatures, as discussed above.
[0019] To combat the problems associated with soluble carbohydrate degradation, the present disclosure provides methods to digest cellulosic biomass solids while effectively furthering the thermal stabilization of soluble carbohydrates produced from them. Specifically, the present disclosure provides methods whereby hydrothermal digestion and one or more catalytic reduction reactions take place in the same vessel. We find that stabilization of soluble carbohydrates occurs more effectively if conducted in this way. The above can be accomplished by including a sludge catalyst capable of activating molecular hydrogen in a hydrothermal digestion unit containing cellulosic biomass solids and transporting the sludge catalyst in the digestion liquor phase to carry out its distribution therein. As used herein, the term "slurry catalyst" refers to a catalyst comprising fluidly mobile catalyst particles that can be at least partially suspended in a fluid phase by means of gas flow, liquid flow, mechanical agitation, or any combination of these. The presence of the sludge catalyst in the hydrothermal digestion unit may allow one or more IN SITU catalytic reduction reactions to occur therein, thereby intercepting and advantageously transforming soluble carbohydrates into a more stable reaction product as soon as possible after the carbohydrates soluble form. As used herein, the term "IN SITU catalytic reduction reaction" refers to a catalytic reduction reaction that takes place in the same vessel as a digestion process. Reaction product formation can reduce the amount of thermal decomposition that occurs during hydrothermal digestion, thereby allowing high-yield conversion of cellulosic biomass solids to a desired reaction product to occur in a timely manner.
[0020] In addition to rapidly stabilizing soluble carbohydrates as a reaction product, conducting one or more IN SITU catalytic reduction reactions can also be particularly advantageous from an energy efficiency standpoint. Specifically, hydrothermal digestion of cellulosic biomass is an endothermic process, whereas catalytic reduction reactions are exothermic. Thus, the excess heat generated by the IN SITU catalytic reduction reaction(s) can be used to trigger hydrothermal digestion, thereby decreasing the amount of additional heat energy input needed to drive the digestion. Since digestion and catalytic reduction occur within the same vessel in the modalities described here, there is minimal opportunity for loss of heat transfer to occur, as would occur if the catalytic reduction reaction(s) had to be conducted in a separate location. Furthermore, in such a configuration, the IN SITU catalytic reduction reaction(s) can provide an increasing supply of the reaction product in the hydrothermal digestion unit, which can serve as the digestion solvent, and/or reset it. Since the reaction product and digestion solvent may be the same, there is no express need to separate and recycle a majority of the digestion solvent before further processing the downstream reaction product, which may be additionally advantageous from one point of view. from an energy efficiency standpoint, as discussed earlier.
[0021] Although conducting one or more IN SITU catalytic reduction reactions may be particularly advantageous from an energy efficiency standpoint and for purposes of stabilizing soluble carbohydrates, successfully executing such a coupled process can be problematic in other respects . A significant problem that can be encountered is that of catalyst distribution in the digesting cellulosic biomass solids. Without proper catalyst distribution being performed, ineffective stabilization of soluble carbohydrates can occur. Specifically, soluble carbohydrates may have a greater opportunity to thermally degrade during the time it takes to reach a catalytic site and undergo catalytic reduction. In contrast, with a well-distributed catalyst, the soluble carbohydrates produced during digestion can be removed less from a catalytic site and can be stabilized more easily. Although a catalyst can be pre-mixed with cellulosic biomass solids or com-mixed with cellulosic biomass solids added in a hydrothermal digestion unit, these solutions can produce inadequate catalyst distribution and present significant engineering challenges that markedly increase the complexity and operating costs of the process. .
[0022] In the methods described here, a sludge catalyst can be delivered into the cellulosic biomass solids using fluid flow to transport the sludge catalyst therein. Although the sludge catalyst can be transported to the cellulosic biomass solids using fluid flow from any direction in the hydrothermal digestion unit, we find it more effective to use upward directed fluid flow to transport the sludge catalyst to the cellulosic biomass solids. Transporting the slurry catalyst to a cellulosic biomass load from the bottom to the top using upward directed fluid flow can have numerous advantages. Specifically, it can overcome gravity and sedimentation-induced compaction that occurs during addition and digestion of cellulosic biomass solids. Sedimentation and compaction of cellulosic biomass solids can impact the fluid flow through the hydrothermal digestion unit and particularly reduce its ability to effectively distribute a slurry catalyst to them. Using upwardly directed fluid flow, sedimentation and compaction problems can be reduced by promoting expansion of the cellulosic biomass charge to let the slurry catalyst be distributed therein. Furthermore, by using upwardly directed fluid flow, there may be less need to use mechanical agitation or similar mechanical agitation means that may otherwise be needed to obtain adequate catalyst distribution. This feature can allow high loadings of cellulosic biomass solids relative to the digestion solvent to be used, thereby increasing production and process economics.
[0023] Use of upward directed fluid flow to deliver a slurry catalyst to cellulosic biomass solids may allow higher cellulosic biomass solids loadings relative to the digestion solvent to be used than would otherwise be possible with other modes of catalyst distribution. The relatively large size of most cellulosic biomass solids (eg 1 mm or more) can produce interstitial voids in a packed or expanded bed of cellulosic biomass solids into which a slurry catalyst can be distributed even at high solids ratios. of cellulosic biomass relative to the digestion solvent. At high ratios of cellulosic biomass solids relative to digestion solvent (eg 10% cellulosic biomass solids relative to solvent or more), a viscous slurry may form, particularly when the biomass particulate size is small, which it may be difficult to mechanically shake or otherwise mechanically disturb. The modalities described herein take advantage of the porosity of the natural bed of cellulosic biomass solids in order to distribute a slurry catalyst therein without the need for mechanical agitation or similar mixing. The ability to use high loadings of cellulosic biomass solids relative to the digestion solvent in the present embodiments can be advantageous from a production standpoint. Specifically, larger amounts of cellulosic biomass solids can be processed per unit size of the hydrothermal digestion unit, thereby increasing the economics of the process. Additionally, smaller volume digestion units, which can be simpler to build and maintain, can also be used without sacrificing production, thereby further aiding process economics.
[0024] As those skilled in the art will appreciate, retention of a slurry catalyst in a defined location is a common problem that can be encountered when using these types of catalysts. Specifically, a finely divided slurry catalyst can flow with a fluid and be difficult to separate through gravity sedimentation alone. A solution to this problem is described in United States patent application 61/665,627, of the same applicant filed on June 28, 2012 entitled "Methods for Hydrothermal Digestion of Cellulosic Biomass Solids in the Presence of a Distributed Sllury Catalyst" filed concurrently with This one. Specifically, in the manner described therein, a slurry catalyst can be recirculated through a cellulosic biomass charge in order to distribute the catalyst therein. Slurry catalyst recirculation can also at least partially address the problem of cellulosic biomass fines, which can co-circulate with the slurry catalyst in some embodiments. There is no need to separate the sludge catalyst from the circulating fluid stream in this case, as an intention of this process is the direct return of the sludge catalyst to the hydrothermal digestion unit.
[0025] Although continuous recirculation of the sludge catalyst into cellulosic biomass solids may address the problem of catalyst distribution therein, in some cases it may be more desirable to retain the sludge catalyst at a fixed location and only perform recirculation instead. periodic. Continuous recirculation may also be undesirable from an energy efficiency standpoint. As discussed below, cellulosic biomass solids can, in some cases, effectively retain a slurry catalyst in them, such that continuous recirculation is not necessary to maintain effective catalyst delivery. In these examples and others, periodic circulation of the slurry catalyst on a necessary basis may be sufficient to maintain good slurry catalyst distribution.
[0026] When the slurry catalyst is not being continuously recirculated through the cellulosic biomass solids, it may still be desirable to remove a reaction product from the hydrothermal digestion unit and further transform the reaction product through downstream reforming reactions. As previously noted, retention of the slurry catalyst in cellulosic biomass solids can be difficult because of their propensity to displace with a fluid stream. In many instances, it may be desirable to remove the slurry catalyst from the reaction product before conducting further transformations therein. Slurry catalyst removed from the reaction product can then be returned to the hydrothermal digestion unit, if desired.
[0027] In cases where sludge catalyst recirculation is not performed, it may be desirable to retain the sludge catalyst in a fixed location and return it only periodically to the cellulosic biomass solids in the hydrothermal digestion unit. One way in which the slurry catalyst can be retained in a fixed location is through the use of an auxiliary filter. Use of an auxiliary filter can let a filter cake build up in a solids retention mechanism, such as a grid or a filter, for example, which effectively sequesters the mud catalyst, but allows a fluid to pass through it without induce an excessive pressure drop. Filter cake formation can protect the solids retention mechanism from fouling by catalyst mud or other fine solids, which can result in costly system downtime and capital costs for replacement, while providing a reaction product that it is free of mud catalyst. After a point of time, the filter cake can be removed from the solids retention mechanism, and the slurry catalyst can then be redistributed to the cellulosic biomass solids using fluid flow.
[0028] We have found that appropriately sized cellulosic biomass solids can be used as a digestible filter aid to promote retention of a sludge catalyst at a desired location during hydrothermal digestion of cellulosic biomass solids. Specifically, such a digestible filter aid can join together to form a filter cake in a solids retention mechanism in proximity to a fluid outlet from the hydrothermal digestion unit. The solids retention mechanism can reside in the hydrothermal digestion unit or be located external to it. The solids retention mechanism can allow solids to be removed from the reaction product leaving the hydrothermal digestion unit, such that solids are less likely to result in downstream process problems. Once formed, the filter cake can at least partially sequester the slurry catalyst therein while allowing the reaction product produced in the hydrothermal digestion unit to continue to flow through it. Additionally, in some embodiments, at least a portion of the digestible filter aid can be distributed completely into the cellulosic biomass solids in such a way that it promotes the retention and distribution of the slurry catalyst therein.
[0029] Since the filter aid used in the modalities described here is digestible, the filter aid particulates may eventually become completely solubilized or shrink in size to the point where they no longer form an effective filter cake in the retention mechanism. of solids. At this point, fluid flow through the solids retention mechanism can be impacted, particularly if the mud catalyst or filter aid itself becomes trapped in the solids retention mechanisms. Although filter aid can sometimes be released from the solids retention mechanism, the slurry catalyst may often not be easily released. Once the filter cake is no longer functioning effectively, the filter cake can be removed from the solids retention mechanism and returned to the cellulosic biomass solids, where the slurry catalyst therein can then be redistributed. Although the filter cake can be removed at this point in time, it should be noted that it can be removed earlier, if desired, to maintain a desired filter cake thickness, to limit excessive pressure drop across the retention mechanism. solids, and/or perform an early return of the mud catalyst to cellulosic biomass solids, for example.
[0030] Once removed from the solids retention mechanism, a new filter cake needs to be formed. An advantage of the processes described here is that fresh digestible filter aid can be formed IN SITU during hydrothermal digestion. Specifically, partial hydrothermal digestion of cellulosic biomass solids can produce partially digested cellulosic biomass solids, which can comprise at least some cellulosic biomass fines. At the same point in hydrothermal digestion, cellulosic biomass fines can fluidly move and be transported to the solids retention mechanism. Thus, as the original digestible filter aid becomes depleted, it can be continually replaced with partially digested cellulosic biomass solids that are generated IN SITU. Essentially, the modalities described here have made the problematic formation of cellulosic biomass fines a suitable resource for retaining the slurry catalyst in a desired location. Although digestible filter aid is produced internally in the modalities described here, it should be understood that the digestible filter aid may, in some embodiments, be supplemented with additional digestible filter aid from an external source. For example, in some embodiments, after removal of the filter cake, it may be desirable to provide a fresh supply of digestible filter aid in close proximity to the solids retention mechanism in order to promote more rapid formation of a new filter cake. Use of an external source of the digestible filter aid can also let the filter aid structure and particulate size be better controlled, thereby promoting optimization of its filtration performance and minimizing the pressure drop across it.
[0031] Although a non-digestible filter aid may be used, at least in principle, to form a filter cake and promote retention of the slurry catalyst, it may be undesirable to do so, particularly for a continuously operating process. Specifically, if fresh nondigestible filter aid has to be added each time a new filter cake is deposited, amounts of nondigestible filter aid can eventually reach problematic levels and undesirably shorten the time period between process maintenance operations . For example, excessive amounts of a nondigestible filter aid can result in less porosity in the cellulosic biomass feed, thereby making it increasingly difficult to distribute the slurry catalyst therein. Furthermore, excessive filter aid can lead to the formation of such a bulky filter cake, where large pressure drops occur and fluid flow is unduly impacted. Still additionally, a continually increasing concentration of nondigestible filter aid may require additional mixing and energy input to maintain its distribution in a fluid and prevent build-up of solids in the digestion unit, any of which can impact the economics of the digestion process. . On the contrary, by digesting existing filter aid and continuously forming a new one, as in the modalities described here, the total amount of filter aid can be kept within acceptable limits in order to avoid the above and other problems.
[0032] Although conducting one or more IN SITU catalytic reduction reactions may be highly desirable for the purpose of stabilizing soluble carbohydrates and achieving thermal integration, catalyst poisons and other substances in cellulosic biomass can make implementing such a process very difficult. When conducting an IN SITU catalytic reduction reaction, there is no opportunity to remove catalyst poisons before they contact the distributed sludge catalyst. One way in which this problem can be approached is to use a poison tolerant slurry catalyst, some of which are discussed below. Another alternative is to use a sludge catalyst that is regenerable upon exposure to conditions that can easily be established in or near the hydrothermal digestion unit. For example, in some embodiments, a regenerable slurry catalyst can be regenerated by exposure to water at a temperature of at least 300°C.
[0033] Yet another alternative to address the problem of catalyst poisoning is to conduct the digestion of cellulosic biomass solids in stages. Many of the poisons that can deactivate a sludge catalyst arise from compounds containing sulfur and nitrogen in crude cellulosic biomass solids, particularly amino acids. Compounds containing sulfur and nitrogen, along with hemicellulose and lignin, can be at least partially removed from cellulosic biomass solids at lower digestion temperatures than those at which cellulose produces soluble carbohydrates. By controlling the digestion temperature, a biomass pulp can be produced that is enriched in cellulose, but depleted in catalyst poisons that can undesirably affect the catalytic activity, thereby allowing hydrothermal digestion of the biomass pulp to occur with less impact in catalytic activity. Notably, the biomass pulp so produced may comprise at least a portion of the digestible filter aid described herein in some embodiments. For example, all or part of the cellulosic biomass solids introduced into the hydrothermal digestion unit can be at least partially digested to remove catalyst poisons and other undesirable materials prior to conducting hydrothermal digestion and the IN SITU catalytic reduction reaction. Thus, in some modalities, the digestible filter aid can be carried out on the cellulosic biomass solids prior to their introduction into the hydrothermal digestion unit. In some embodiments, digestible filter aid can be formed by grinding or otherwise reducing the size of cellulosic biomass solids.
[0034] Unless otherwise specified herein, it is to be understood that use of the terms "biomass" or "cellulosic biomass" in the description herein refers to "cellulosic biomass solids." Solids can be of any size, shape or shape. Cellulosic biomass solids can be natively present in any of these solid sizes, shapes, or shapes, or they can be further processed prior to hydrothermal digestion. In some embodiments, cellulosic biomass solids can be chopped, ground, shredded , pulverized and the like to produce a desired size prior to hydrothermal digestion. In some embodiments, at least a portion of the cellulosic biomass solids introduced into the hydrothermal digestion unit may be of a suitable size to serve as a digestible filter aid, which may promote sludge catalyst sequestration. In some modalities, cellulosic biomass solids that serve as the filter digest aid may be natively present in bulky cellulosic biomass solids. In some or other embodiments, cellulosic biomass solids that serve as the digestible filter aid can be blended with the bulk cellulosic biomass solids. In some or other embodiments, cellulosic biomass solids can be washed (eg, with water, an acid, a base, combinations of these, and the like) before hydrothermal digestion takes place.
[0035] In the practice of the present embodiments, any type of suitable cellulosic biomass source can be used. Suitable cellulosic biomass sources may include, for example, forest waste, agricultural waste, herbaceous material, municipal solid waste, recycled waste and paper, pulp and paper mill waste, and any combination thereof. Thus, in some embodiments, a suitable cellulosic biomass may include, for example, corn fodder, straw, bagasse, miscanthus, sorghum residue, grass, bamboo, water hyacinth, hardwood, hardwood chips, hardwood pulp , softwood, softwood chips, softwood pulp, and any combination of these. Leaves, roots, seeds, stems, bark and the like can be used as a source of cellulosic biomass. Common sources of cellulosic biomass can include, for example, agricultural residues (eg corn stalks, straw, seed husks, sugar cane residues, walnut shells and the like), wood materials (eg wood or bark tree, sawdust, hardwood branch, mill scrap and the like), municipal waste (eg waste paper, yard shavings or debris and the like), and energy crops (eg poplars, willows, grass, alfalfa, turkey grass meadow, corn, soybeans and the like). Cellulosic biomass can be chosen based on considerations such as, for example, cellulose and/or hemicellulose content, lignin content, growing time/season, growing location/transport cost, growing costs, harvesting costs and the like .
[0036] Illustrative carbohydrates that may be present in cellulosic biomass solids include, for example, sugars, sugar alcohols, celluloses, lignocelluloses, hemicelluloses, and any combination thereof. Since soluble carbohydrates were produced through hydrothermal digestion according to the modalities described here, the soluble carbohydrates can be transformed into a more stable reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof, by means of one or more catalytic reduction reactions. In some embodiments, the reaction product can be further reformed into a biofuel using any combination of hydrogenolysis reactions and/or additional hydrogenation reactions, condensation reactions, isomerization reactions, oligomerization reactions, hydrotreatment reactions, alkylation reactions, and similar.
[0037] In some embodiments, methods described here may comprise: providing cellulosic biomass solids and a slurry catalyst in a hydrothermal digestion unit, the slurry catalyst being capable of activating molecular hydrogen ("Molecular Hydrogen Activating Slurry Catalyst" "); providing a digestible filter aid in the hydrothermal digestion unit; distributing the slurry catalyst into the cellulosic biomass solids using fluid flow; retaining at least a portion of the slurry catalyst in a fixed location using the digestible filter aid; heating the cellulosic biomass solids in the hydrothermal digestion unit in the presence of sludge catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; and performing a first catalytic reduction reaction on soluble carbohydrates in the hydrothermal digestion unit, thereby at least partially forming a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof in the hydrothermal digestion unit .
[0038] In some embodiments, methods described here may comprise: providing cellulosic biomass solids and a slurry catalyst in a hydrothermal digestion unit, the slurry catalyst being capable of activating molecular hydrogen ("Molecular Hydrogen Activating Slurry Catalyst" ") and cellulosic biomass solids comprising a digestible filter aid comprising cellulosic biomass particulates capable of forming a filter cake suitable for retaining at least a portion of the sludge catalyst therein; distribute the slurry catalyst into the cellulosic biomass solids using upward directed fluid flow; heating the cellulosic biomass solids in the hydrothermal digestion unit in the presence of sludge catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; allowing a portion of the liquor phase to exit the hydrothermal digestion unit; forming a filter cake comprising the digestible filter aid in a solids retention mechanism configured to let the liquor phase pass therethrough; collecting at least a portion of the slurry catalyst in the filter cake; and performing a first catalytic reduction reaction on soluble carbohydrates in the hydrothermal digestion unit, thereby at least partially forming a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof in the hydrothermal digestion unit .
[0039] In some embodiments, heating of cellulosic biomass solids can occur while the hydrothermal digestion unit is in a pressurized state. As used herein, the term "pressurized state" refers to a pressure that is greater than atmospheric pressure (1 bar / 100 kPa). Heating a digestion solvent in a pressurized state can allow the normal boiling point of the digestion solvent to be exceeded, thereby allowing the hydrothermal digestion rate to be increased relative to lower temperature digestion processes. In some embodiments, heating of cellulosic biomass solids in the hydrothermal digestion unit can occur at a pressure of at least 30 bar (3,000 kPa). In some embodiments, heating of the cellulosic biomass solids in the hydrothermal digestion unit can take place at a pressure of at least 60 bar (6000 kPa), or at a pressure of at least 90 bar (9,000 kPa). In some modalities, heating of cellulosic biomass solids in the hydrothermal digestion unit can occur at a pressure ranging between 30 bar (3000 kPa) and 430 bar (43,000 kPa). In some embodiments, heating of cellulosic biomass solids in the hydrothermal digestion unit can occur at a pressure ranging from 50 bar (5,000 kPa) to 330 bar (33,000 kPa), or at a pressure ranging from 70 bar (7,000 kPa) to 130 bar (13,000 kPa), or at a pressure ranging between 30 bar (3,000 kPa) and 130 bar (13,000 kPa).
[0040] In some embodiments, cellulosic biomass solids can be maintained at a pressure of at least 30 bar (3,000 kPa) and heated to a temperature of at least 150°C. In some embodiments, cellulosic biomass solids can be maintained at a pressure of at least 70 bar (7,000 kPa), or at least 100 bars (10,000 kPa), and heated to a temperature of at least 150°C. In some or other embodiments, cellulosic biomass solids can be heated to a temperature of at least 200°C, or at least 250°C, or at least 300°C.
[0041] In some embodiments, the cellulosic biomass solids and the sludge catalyst can be supplied in the hydrothermal digestion unit at the same time. For example, in some embodiments, a mixture of cellulosic biomass solids and the sludge catalyst can be simultaneously introduced into the hydrothermal digestion unit. In other embodiments, the cellulosic biomass solids and the sludge catalyst can be added at the same time in separate feeds in the hydrothermal digestion unit. When introduced into the hydrothermal digestion unit at the same time as the cellulosic biomass solids, the slurry catalyst can either be distributed into the cellulosic biomass solids or it can remain undistributed.
[0042] In some embodiments, the cellulosic biomass solids and the slurry catalyst can be supplied in the hydrothermal digestion unit separately. In some embodiments, the slurry catalyst can be supplied to the hydrothermal digestion unit before the cellulosic biomass solids are supplied. For example, during process start-up, slurry catalyst can be supplied to the hydrothermal digestion unit before cellulosic biomass solids are supplied. In some embodiments, the sludge catalyst can be placed at or near the base of the hydrothermal digestion unit, and a load of cellulosic biomass solids can be placed on the sludge catalyst below. Placing the sludge catalyst in the hydrothermal digestion unit before the cellulosic biomass solids can position the sludge catalyst in such a way that it can be delivered into the cellulosic biomass solids using upwardly directed fluid flow. In some embodiments, the slurry catalyst may be present in the hydrothermal digestion unit, optionally along with partially digested cellulosic biomass solids, while fresh cellulosic biomass solids are added to it.
[0043] In some embodiments, the hydrothermal digestion unit may be loaded with a fixed amount of sludge catalyst, while cellulosic biomass solids are continuously or semi-continuously fed into it, thereby allowing hydrothermal digestion to occur in a continuous manner. That is, fresh cellulosic biomass solids can be added to the hydrothermal digestion unit on a continuous basis or as needed in order to replenish cellulosic biomass solids that have been digested to form soluble carbohydrates. In some embodiments, cellulosic biomass solids can be continuously or semi-continuously supplied to the hydrothermal digestion unit while the hydrothermal digestion unit is in a pressurized state. In some embodiments, the pressurized state may comprise a pressure of at least 30 bar (3,000 kPa). Without the ability to introduce fresh cellulosic biomass into a pressurized hydrothermal digestion unit, depressurization and cooling of the hydrothermal digestion unit can occur during addition of biomass, significantly reducing the energy efficiency and cost of the biomass conversion process. As used herein, the term "continuous addition" and its grammatical equivalents will refer to a process in which cellulosic biomass solids are added to a hydrothermal digestion unit in an uninterrupted manner without fully depressurizing the hydrothermal digestion unit. As used herein, the term "semi-continuous addition" and its grammatical equivalents will refer to a discontinuous but necessary addition of cellulosic biomass solids in a hydrothermal digestion unit without fully depressurizing the hydrothermal digestion unit. Means by which cellulosic biomass solids can be added continuously or semi-continuously into a pressurized hydrothermal digestion unit are discussed in more detail below.
[0044] In some embodiments, cellulosic biomass solids being continuously or semi-continuously added to the hydrothermal digestion unit may be pressurized before being added to the hydrothermal digestion unit, particularly when the hydrothermal digestion unit is in a pressurized state. Pressurization of the cellulosic biomass solids from atmospheric pressure to a pressurized state may occur in one or more pressurization zones prior to the addition of the cellulosic biomass solids to the hydrothermal digestion unit. Suitable pressurization zones that can be used to pressurize and introduce solids from cellulosic biomass to a pressurized hydrothermal digestion unit are described in more detail in the same applicant's United States patent application publications 2013/0152457 and 2013/0152458, each filed December 20, 2011. Suitable pressurization zones in the manner described herein may include, for example, pressure vessels, pressurized auger feeders, and the like. In some embodiments, multiple pressurization zones can be connected in series to increase the pressure of cellulosic biomass solids in a stepwise manner.
[0045] In some embodiments, providing the digestible filter aid in the hydrothermal digestion unit may comprise forming the digestible filter aid in the hydrothermal digestion unit by heating the cellulosic biomass solids in the presence of the digestion solvent. That is, in such embodiments, the digestible filter aid can be formed IN SITU in the hydrothermal digestion unit. In some embodiments, the methods may further comprise adding an additional amount of the digestible filter aid to the hydrothermal digestion unit while the digestible filter aid is being formed therein.
[0046] In some embodiments, providing the digestible filter aid to the hydrothermal digestion unit may comprise adding the digestible filter aid to the hydrothermal digestion unit. In some embodiments, the digestible filter aid can be added when the cellulosic biomass solids therein no longer contain existing cellulosic biomass particulates or another suitable digestible filter aid to form a filter cake. In other embodiments, digestible filter aid may be added to the hydrothermal digestion unit to supplement an existing amount of digestible filter aid present or being produced therein.
[0047] When starting the processes described by the various methods presented here, it may be desirable to provide digestible filter aid in the hydrothermal digestion unit prior to commencing slurry catalyst distribution. In various embodiments, the digestible filter aid can be added separately from the slurry catalyst and/or cellulosic biomass solids, or together with them. In some embodiments, digestible filter aid can be added to the hydrothermal digestion unit with the cellulosic biomass solids. In some embodiments, cellulosic biomass solids can natively contain at least some cellulosic biomass solids of a suitable size to promote retention of the slurry catalyst at a fixed location (eg, through formation of a filter cake). In some or other embodiments, cellulosic biomass solids can be processed prior to their introduction into the hydrothermal digestion unit in such a way that at least a portion of the cellulosic biomass solids is of a suitable size to promote retention of the sludge catalyst in one location fixed. In some or other embodiments, separate feeds of digestible filter aid and cellulosic biomass solids can be introduced into the hydrothermal digestion unit.
[0048] After starting the process, digestible filter aid can be produced during hydrothermal digestion of cellulosic biomass solids, in some modalities. In the manner described above, hydrothermal digestion of cellulosic biomass solids can produce cellulosic biomass particulates of a suitable size to serve as a digestible filter aid. In some embodiments, the cellulosic biomass particulates that serve as the digestible filter aid may comprise cellulosic biomass fines. The digestible filter aid being produced can replace or supplement the one originally present and now being consumed by hydrothermal digestion. In some or other embodiments, additional digestible filter aid may be introduced into the hydrothermal digestion unit to supplement that produced during hydrothermal digestion of the cellulosic biomass solids.
[0049] It is believed that the digestible filter aid used in the present embodiments, especially that used to start the process, is not particularly limited. In general, any material that can promote sludge catalyst retention and become solubilized at an adequate rate in the digestion solvent without producing undesirable materials that can, for example, sludge catalyst poison, foul the hydrothermal digestion unit and/or interfere in downstream reforming reactions it can be used as the digestible filter aid. Suitable materials can include, for example, thermally or hydrolytically degradable polymers, slowly soluble inorganic or organic compounds, salts, sugars, combinations thereof and the like. In some embodiments, the filter aid used to start the process may comprise a non-digestible filter aid, with digestible filter aid being produced later by digesting the cellulosic biomass solids. It is believed that initial use of a non-digestible filter aid does not lead to problematic filter aid constitution.
[0050] In some embodiments, the digestible filter aid can be derived from cellulosic biomass solids. In some embodiments, the digestible filter aid can comprise partially digested cellulosic biomass solids (e.g., a biomass pulp). In some embodiments, the digestible filter aid may comprise a low value cellulosic material such as, for example, sawdust, ground straw, shredded paper, and the like. In some or other embodiments, the digestible filter aid can comprise cellulosic biomass fines. In some embodiments, biomass pulp and/or cellulosic biomass fines can be formed external to the hydrothermal digestion unit and added thereto (e.g., during process start-up and/or to supplement digestible filter aid formed during hydrothermal digestion). Forming a digestible filter aid from cellulosic biomass external to the hydrothermal digestion unit can be advantageous from the standpoint of limiting the introduction of catalyst poisons and other undesirable materials into the hydrothermal digestion unit. In some or other embodiments, after starting the process, formation of the digestible filter aid may occur IN SITU in the hydrothermal digestion unit while hydrothermal digestion of the cellulosic biomass solids takes place.
[0051] In some embodiments, cellulosic biomass solids comprising the digestible filter aid may have a particulate size of at most 5 mm. In other embodiments, cellulosic biomass solids comprising the digestible filter aid may have a particulate size of at most 4 mm, or at most 3 mm, or at most 2 mm, or at most 1 mm, or at most 900 μm, or at most 800 μm, or at most 700 μm, or at most 600 μm, or at most 500 μm, or at most 400 μm, or at most 300 μm, or at most 200 μm, or at most 100 μm. In some embodiments, cellulosic biomass solids comprising the digestible filter aid may have a particulate size ranging between 3 mm and 10 µm or between 100 µm and 10 µm. In general, the largest particle size suitable for forming a filter cake will be determined by a pore size present in the solids retention mechanism. In some embodiments, the digestible filter aid can comprise a plurality of particulate sizes. Use of a filter aid comprising a variety of particulate sizes can promote the formation of a more robust filter cake. In some embodiments, cellulosic biomass solids comprising the digestible filter aid can comprise cellulosic biomass fines. Specifically, in some embodiments, the digestible filter aid may comprise cellulosic biomass particulates with a particulate size of at most 3 mm, which are formed by heating the cellulosic biomass solids in the presence of the digestion solvent.
[0052] In various embodiments described herein, upward directed fluid flow can be used to distribute the slurry catalyst into the cellulosic biomass solids. As used herein, the terms "distribute", "distribution" and variants thereof refer to a condition in which a slurry catalyst is spread over at least a portion of the height of a cellulosic biomass feed and not all concentrated. in one location. No particular degree of distribution is implied by use of the term "distributes" or its variants. In some embodiments, the slurry catalyst can be fully delivered at the time of the cellulosic biomass charge. In other embodiments, the slurry catalyst can be fully distributed in only a portion of the cellulosic biomass feed. In some embodiments, the distribution may comprise a substantially homogeneous distribution, such that a slurry catalyst concentration is substantially the same at all times of a cellulosic biomass feed. In other embodiments, the distribution may comprise a heterogeneous distribution such that different concentrations of the slurry catalyst are present at different heights of the cellulosic biomass load. When a heterogeneous distribution of the sludge catalyst is present, the concentration of the sludge catalyst in the cellulosic biomass solids may increase top to bottom in some embodiments or decrease top to bottom in other embodiments. In some embodiments, the upward directed fluid flow velocity can be used to modulate the type of slurry catalyst distribution obtained.
[0053] In some embodiments, upward directed fluid flow may begin before heating of the cellulosic biomass solids begins. Specifically, in some embodiments, distribution of the slurry catalyst can occur prior to formation of a liquor phase comprising soluble carbohydrates. In other embodiments, heating of the cellulosic biomass solids can begin before the upward directed fluid flow begins. While it is generally desirable to deliver the slurry catalyst to the cellulosic biomass solids before soluble carbohydrate production occurs, some degree of heating prior to slurry catalyst delivery may be tolerable in some embodiments. For example, if desired, the cellulosic biomass solids may first be heated to a temperature that is not sufficient to produce and/or degrade soluble carbohydrates before beginning the upwardly directed fluid flow to distribute the slurry catalyst. Reasons why cellulosic biomass solids can be heated to a temperature below that at which soluble carbohydrates are produced may include, for example, removal of non-cellulosic materials, including catalyst poisons, from the cellulosic biomass. Furthermore, since the hydrothermal digestion processes described herein can occur continuously, in some embodiments, the sludge catalyst can get distributed into fresh cellulosic biomass solids that are being carried to the hydrothermal digestion unit while hydrothermal digestion and formation of soluble carbohydrate remain in the cellulosic biomass solids already present in them.
[0054] In various embodiments, the upwardly directed fluid flow may comprise one or more upwardly directed fluid streams. In various embodiments, one or more upwardly directed fluid streams may pass through the cellulosic biomass solids, carrying the slurry catalyst therein, and one or more upwardly directed fluid streams may subsequently exit the hydrothermal digestion unit. In some embodiments, the upwardly directed fluid flow may comprise an upwardly directed fluid stream. In some embodiments, the upwardly directed fluid flow may comprise two upwardly directed fluid streams, or three upwardly directed fluid streams, or four upwardly directed fluid streams, or five upwardly directed fluid streams. In some embodiments, one or more upwardly directed fluid streams can comprise a gas stream, a liquid stream, or any combination thereof.
[0055] In some embodiments, the upwardly directed fluid stream may comprise a gas stream. For example, in some embodiments, a gas stream being used for upward directed fluid flow may comprise a molecular hydrogen stream. In some or other embodiments, steam, long air, or an inert gas such as nitrogen, for example, can be used in place of or in addition to a stream of molecular hydrogen. Up to 40% of steam can be present in the fluid stream in various modalities. Although a gas stream can carry the sludge catalyst through the cellulosic biomass solids, progression of the sludge catalyst in the hydrothermal digestion unit is generally capped by the level of liquid therein. That is, under ordinary circumstances a gas stream is generally not sufficient to carry the slurry catalyst out of the hydrothermal digestion unit.
[0056] In some embodiments, the upwardly directed fluid stream may comprise a liquid stream. Unlike a gas stream described above, a liquid stream can, in some embodiments, carry the sludge catalyst through the cellulosic biomass solids and potentially out of the hydrothermal digestion unit, as the liquid stream increases the level. of liquid in it. Liquid coming out of the hydrothermal digestion unit can carry the slurry catalyst with it. In the manner described herein, it may be desirable to sequester the sludge catalyst before or after it leaves the hydrothermal digestion unit and eventually recycle the sludge catalyst into the cellulosic biomass solids. In some embodiments, the liquid stream can comprise a stream of digestion solvent. In some embodiments, the digestion solvent can comprise the reaction product formed in the hydrothermal digestion unit.
[0057] In some embodiments, the methods described herein may further comprise retaining the cellulosic biomass solids in the hydrothermal digestion unit by use of a retaining structure. The retention structure may allow digestion solvent, filter aid, sludge catalyst, and other types of small particulates to pass through, but may not have sufficient porosity to let bulky cellulosic biomass solids pass through. Use of a retaining structure can be beneficial, for example, when upwardly directed fluid flow used to distribute the slurry catalyst improperly fluidizes the cellulosic biomass solids. Use of the retaining structure can allow a fluid outlet from the hydrothermal digestion unit to remain unblocked by bulky cellulosic biomass solids, for example. Suitable retaining structures may include, for example, a screen or similar grid-like structure, a frit (for example, a metal or glass frit), a filter, a mat, a porous plate, or the like.
[0058] In some embodiments, the methods described herein may further comprise allowing a portion of the liquor phase to exit the hydrothermal digestion unit, forming a filter cake comprising the digestible filter aid in a solids retention mechanism configured to allow the liquor phase passes through them, and collects at least a portion of the mud catalyst in the filter cake. In various embodiments, allowing a portion of the liquor phase to exit the hydrothermal digestion unit may comprise draining the liquor phase from the hydrothermal digestion unit. In various embodiments, the solids retention mechanism can comprise a screen or similar grid-like structure, a filter, a frit, a membrane, or similar porous medium through which the liquor phase can pass.
[0059] During or after the exit of the liquor phase from the hydrothermal digestion unit, the sludge catalyst can be removed from the liquor phase by collecting in the filter cake. In some embodiments, the slurry catalyst can be collected and retained while still remaining in the hydrothermal digestion unit. Specifically, in some embodiments, the solids retention mechanism may reside in the hydrothermal digestion unit. In other embodiments, the sludge catalyst can be collected and retained outside the hydrothermal digestion unit. Specifically, in some embodiments, the solids retention mechanism may reside outside the hydrothermal digestion unit. For example, in some embodiments, the solids retention mechanism may be in fluid communication with a fluid conduit exiting the hydrothermal digestion unit. Although a similar filter or solids separation mechanism can be used both inside and outside the hydrothermal digestion unit in the modalities described here, use of an externally located solids separation mechanism may be more desirable for maintenance purposes. Furthermore, as discussed below, a filter cake removed from an externally located filter can be more easily returned to the base of a cellulosic biomass feed for purposes of catalyst redistribution.
[0060] In some embodiments, the methods described herein may further comprise removing the filter cake from the solids retention mechanism, and returning at least a portion of the slurry catalyst to the cellulosic biomass solids. In some embodiments, removing the filter cake may comprise reversing fluid flow through the solids retention mechanism to "blow back" the filter aid and mud catalyst from its surface. In some or other embodiments, removing the filter cake may comprise applying cross-flow to the filter cake in order to affect its removal. After filter cake removal, in some embodiments, the methods may further comprise returning at least a portion of the slurry catalyst to the cellulosic biomass solids. In some embodiments, at least a portion of the slurry catalyst may be returned to the top of the cellulosic biomass solids in the hydrothermal digestion unit. In some or other embodiments, at least a portion of the slurry catalyst may be returned to the cellulosic biomass solids base in the hydrothermal digestion unit.
[0061] When the solids retention mechanism is located internally in the hydrothermal digestion unit, filter cake removal can return directly from the mud catalyst to the cellulosic biomass solids. In general, the slurry catalyst is returned near the same height at which it was collected, and catalyst redistribution can take place through continuous fluid mixing in the hydrothermal digestion unit. Conversely, when the solids retention mechanism is located external to the hydrothermal digestion unit, removal of the filter cake thereof can return directly from the slurry catalyst to the hydrothermal digestion unit via the fluid path through which it originally dislodged. or via a different return path. Specifically, in some embodiments, when the solids retention mechanism is external to the hydrothermal digestion unit, the filter cake can be removed therefrom, and the slurry catalyst can be routed back to the base of the hydrothermal digestion unit for redistribution. subsequent to cellulosic biomass solids. Return of filter cake from an external solids retention mechanism can advantageously promote filter cake breakage, thereby facilitating the redistribution of slurry catalyst and filter aid once returned to the hydrothermal digestion unit. In alternative embodiments, at least a portion of the slurry catalyst can be removed from the system. Removal may be desirable, for example, if the slurry catalyst needs to be regenerated.
[0062] Unless otherwise measures are taken, the solids retention mechanism may be at the same temperature as the liquor phase passing through it. Thus, in some embodiments, the filter cake can be at least partially digested while in the solids retention mechanism. To maintain the filter cake for a longer period of time, in some embodiments it may be desirable to moderate the digestion rate of the digestible filter aid comprising the filter cake. Specifically, in some embodiments, the solids retention mechanism can be kept at a lower temperature than that used during digestion in order to reduce the digestion rate of the filter cake disposed therein and otherwise protect the mechanism from retention of solids. In some embodiments, the solids retention mechanism can be maintained at a temperature of 150°C or below. In some embodiments, the solids retention mechanism can be maintained at a temperature of 140°C or below, or 130°C or below, or 120°C or below, or 110°C or below, or 100°C or below .
[0063] In some or other embodiments, it may be desirable to maintain the solids retention mechanism at a temperature higher than that at which digestion is taking place. Although a higher temperature in the solids retention mechanism can promote premature filter cake digestion, heating can reduce the likelihood of precipitation of cellulosic biomass components such as, for example, lignins and tars in the solids retention mechanisms.
[0064] In some embodiments, in addition to forming a filter cake, at least a portion of the digestible filter aid can be distributed in the cellulosic biomass solids, where it can promote retention of the slurry catalyst therein. Again, no particular degree of distribution should be implied by use of the term "distribute". In some embodiments, the digestible filter aid may be homogeneously distributed over cellulosic biomass solids. In other embodiments, the digestible filter aid may be heterogeneously distributed in cellulosic biomass solids Thus, in some embodiments, the digestible filter aid can advantageously promote catalyst retention in the cellulosic biomass solids during the time the catalyst is being circulated through them.
[0065] In the manner described above, the methods described herein can produce additional digestible filter aid through IN SITU hydrothermal digestion of cellulosic biomass solids in order to replace that consumed by hydrothermal digestion. In some embodiments, the methods described herein may comprise further dissolving at least a portion of the digestible filter aid. In more specific embodiments, the methods may comprise dissolving at least a portion of the digestible filter aid while forming fresh digestible filter aid, where the fresh digestible filter aid comprises cellulosic biomass particulates with a particulate size of at most 3 mm, which are formed by heating the cellulosic biomass solids in the presence of the digestion solvent.
[0066] In some embodiments, at least a portion of the slurry catalyst may be fluidly suspended in the digestion solvent by the upwardly directed fluid flow. As used herein, the term "fluidically suspended" refers to the condition that exists when the velocity of the upwardly directed fluid flow matches the terminal velocity of the mud catalyst particulates. In this way, fluidly suspended sludge catalyst particulates neither descend to the base of the hydrothermal digestion unit nor pass completely through the top of a cellulosic biomass charge, carried by the upwardly directed fluid flow. In some embodiments of the methods described herein, a portion of the slurry catalyst can be fluidly suspended and a portion of the slurry catalyst can be transported through the cellulosic biomass solids, and subsequently collected in a filter cake formed by the digestible filter aid. Mud catalyst particulates can be transported through the cellulosic biomass solids by the upward directed fluid flow, if the upward directed fluid flow velocity exceeds the terminal velocity of the mud catalyst particulates. In additional embodiments, a portion of the slurry catalyst may remain at the base of the hydrothermal digestion unit, even when another portion of the slurry catalyst is fluidly suspended. Achieving a fluidly suspended state for the slurry catalyst may comprise sizing the slurry catalyst particulates to match a desired upwardly directed fluid flow velocity, adjusting the upwardly directed fluid flow velocity to match the range of particulate sizes present in a given slurry catalyst, or any combination thereof.
[0067] In various embodiments, the first catalytic reduction reaction performed in the hydrothermal digestion unit can occur in the presence of molecular hydrogen. In some embodiments, molecular hydrogen can be supplied externally to the hydrothermal digestion unit. For example, in some embodiments, molecular hydrogen can be supplied with the upward directed fluid flow. In some or other embodiments, molecular hydrogen can be generated internally through the use of an aqueous phase reforming (APR) catalyst. Molecular hydrogen generation using an APR catalyst can occur in the hydrothermal digestion unit in some embodiments or externally in other embodiments.
[0068] In some embodiments, the mud catalyst may comprise a poison tolerant catalyst. Use of a poison tolerant catalyst may be particularly desirable when catalyst poisons are not removed from cellulosic biomass solids before soluble carbohydrate production takes place. As used herein, a "poison tolerant catalyst" is defined as a catalyst that is capable of activating molecular hydrogen without needing to be regenerated or replaced because of low catalytic activity for at least 12 hours of continuous operation. Use of a poison tolerant catalyst can decrease process downtime disadvantages, which are associated with catalyst regeneration/replacement and process restart.
[0069] In some embodiments, suitable poison tolerant catalysts may include, for example, a sulphide catalyst. In some or other embodiments, a nitrided catalyst can be used as a poison tolerant catalyst. Suitable sulphide catalysts for activating molecular hydrogen (Sulfide Molecular Hydrogen Activating Catalysts) are described in the same applicant's United States patent application publications 2012/0317872, 2012/0317873 and 2013/0109896. Sulfitation can occur by treating the catalyst with hydrogen sulfide or an alternative sulfating agent, optionally while the catalyst is disposed on a solid support. In more particular embodiments, the poison tolerant catalyst can comprise a sulphide cobalt molybdate catalyst. We observe that sulphide cobalt molybdate catalysts, depending on the reaction conditions, can produce C2 - C6 monohydric alcohols, diols (including glycols), triols, and combinations thereof, while not forming an excessive amount of C2 - C4 alkanes . As used herein, the term "monohydric alcohol" refers to an organic molecule containing a single alcohol functional group. Monohydric alcohols formed can be easily separated from water by flash vaporization or liquid-liquid phase separation, and undergo condensation-oligomerization reactions in separate steps over an acid or base catalyst to produce liquid biofuels in the range of gasoline, jet or diesel. Mud catalysts containing Pt or Pd can also be particularly useful poison tolerant catalysts for use in the present embodiments.
[0070] In some embodiments, slurry catalysts suitable for use in the methods described herein can be sulphided by dispersing a slurry catalyst in a fluid phase and adding a sulfating agent to it. Suitable sulphide agents can include, for example, organic sulfoxides (eg, dimethyl sulfoxide), hydrogen sulfide, hydrogen sulfide salts (eg, NaSH) and the like. In some embodiments, the slurry catalyst can be concentrated in the fluid phase after sulfation and then added to the hydrothermal digestion unit.
[0071] In some embodiments, the slurry catalyst may be regenerable. For example, in some embodiments, the slurry catalyst can be regenerated by exposure to water at a temperature above its normal boiling point. As used herein, a "regenerable catalyst" can have at least part of its catalytic activity restored through regeneration, even when poisoned with nitrogen compound impurities, sulfur compound impurities, or any combination thereof. Ideally, such regenerable catalysts should be regenerable with a minimal amount of process downtime. In some embodiments, the slurry catalyst can be regenerated by exposure to water having a temperature of at least 200°C. In some embodiments, the slurry catalyst can be regenerated by exposure to water having a temperature of at least 250°C, or at least 300°C, or at least 350°C, or at least 400°C. The water used to regenerate the mud catalyst can be in a subcritical state or a supercritical state. A particularly suitable slurry catalyst that can be regenerated through exposure to water above its normal boiling point is ruthenium disposed on a solid support such as, for example, ruthenium on titanium dioxide or ruthenium on carbon. Other suitable slurry catalysts can include a platinum or palladium compound disposed on a solid support. Most catalysts effective to mediate a catalytic reduction reaction are also regenerable, at least in part, through heat treatments with hydrogen. Slurry catalyst regeneration can take place in the hydrothermal digestion unit or elsewhere if desired.
[0072] In various embodiments, the slurry catalyst can have a particulate size of 250 microns or less. In some embodiments, the slurry catalyst can have a particulate size of 100 microns or less. In some embodiments, the slurry catalyst can have a particulate size of 10 microns or less. In some embodiments, the minimum slurry catalyst particulate size can be 1 micron. In some embodiments, the slurry catalyst can comprise catalyst fines in the processes described herein. As used herein, the term "catalyst fines" refers to solid catalysts with a nominal particulate size of 100 microns or less. Catalyst fines can be generated from catalyst production processes, for example, during solid catalyst extrusion. Catalyst fines can also be produced by grinding larger catalyst solids or during catalyst solids regeneration. Suitable methods for making catalyst fines are described in US patents 6,030,915 and 6,127,299. In some cases, catalyst fines can be removed from a solid catalyst production run, as they can be difficult to sequester in some catalytic processes. Techniques for removing catalyst fines from large catalyst solids can include, for example, sieving size separation processes or the like. Since there is no requirement to retain the catalyst in a fixed location in the modalities described here, catalyst fines can be particularly well tolerated. Advantageously, because of their small size, catalyst fines can be easily fluidized and completely distributed into cellulosic biomass solids.
[0073] In some embodiments, the mud catalyst may be operable to generate molecular hydrogen. For example, in some embodiments, catalysts suitable for reforming the aqueous phase (i.e., APR catalysts) can be used. Suitable APR catalysts can include, for example, catalysts comprising platinum, palladium, ruthenium, nickel, cobalt or other Group VIII metals bonded or modified with rhenium, molybdenum, tin or other metals. Thus, in some embodiments described here, an external hydrogen feed may not be necessary. However, in other embodiments, an external hydrogen feed can be used, optionally in combination with internally generated hydrogen.
[0074] In addition to fluidizing the slurry catalyst and digestible filter aid, the fluid flow directly upward can fluidize cellulosic biomass solids in some modalities. In other embodiments, the upwardly directed fluid flow does not substantially fluidize the cellulosic biomass solids. In some embodiments, the upward directed fluid flow velocity may be sufficient to fluidize the digestible filter aid and slurry catalyst, but not the bulky cellulosic biomass solids. Those skilled in the art will know how to choose an appropriate upward directed fluid flow velocity suitable for a given application depending on whether they wish to fluidize the cellulosic biomass solids in combination with the slurry catalyst and digestible filter aid.
[0075] In some embodiments, the upward directed fluid flow can at least partially expand the cellulosic biomass solids in the hydrothermal digestion unit. As used herein, the terms "at least partially expand" and "at least partially expand" refer to a condition in which the packing density of cellulosic biomass solids is reduced by upwardly directed fluid flow. At least partial expansion of the cellulosic biomass solids can be beneficial to ensure good distribution of the slurry catalyst therein and/or to reduce the likelihood of blockages occurring in the hydrothermal digestion unit.
[0076] In some cases it may be desirable to conduct additional catalytic reduction reactions on the reaction product (eg, triols, diols, and/or monohydric alcohols) produced in the hydrothermal digestion unit. For example, it may be desirable to carry out additional hydrogenolysis reactions to reduce the molecular weight of the reaction products, or it may be desirable to effect a further reduction in the degree of oxygenation of the reaction product. In some embodiments, the methods described herein may further comprise performing a second catalytic reduction reaction on the liquor phase exiting the hydrothermal digestion unit so as to further form the reaction product. For example, in some embodiments, the reaction product formed in the hydrothermal digestion unit can be transferred from the hydrothermal digestion unit to a reactor configured to conduct a catalytic reduction reaction, where the degree of oxygenation of the reaction product can be further decreased . Specifically, in some embodiments, the second catalytic reduction reaction can be used to increase the amount of monohydric alcohols present in the reaction product. In some embodiments, at least a portion of the reaction product produced in the second catalytic reduction reaction can be recirculated to the hydrothermal digestion unit.
[0077] In other embodiments, the reaction product from the hydrothermal digestion unit can be processed directly into the fuel mixtures without performing a second catalytic reduction reaction on it. Since the liquor phase extraction from the hydrothermal digestion unit has had sludge catalyst removed from it, the liquor phase can be used directly, if desired, in such downstream reforming reactions.
[0078] During the performance of a second catalytic reduction reaction, the catalyst used in the reactor may be the same or different from that used in the hydrothermal digestion unit. In some embodiments, the catalyst used to carry out the second catalytic reduction reaction can be a slurry catalyst, which can be the same slurry catalyst used in the hydrothermal digestion unit or a different slurry catalyst. In other embodiments, the catalyst used to carry out the second catalytic reduction reaction may be different. In some embodiments the catalyst used to conduct the second catalytic reduction reaction can comprise a fixed bed catalyst, a bubbling bed catalyst, a fluid bed catalyst, or the like.
[0079] In some embodiments, one or more separation or purification steps may be employed after the liquor phase exits the hydrothermal digestion unit. Separation or purification steps that can be performed include, for example, ion exchange, flash distillation, adsorption and the like. Then, further transformation of the reaction product can take place.
[0080] Application of the methods described here can allow high percentages of a cellulosic biomass load to be solubilized by digestion. In some embodiments, at least 60% of the cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 70% of the cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 80% of the cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 90% of the cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 95% of the cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 97% of the cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 99% of cellulosic biomass solids, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates.
[0081] In some or other embodiments, at least 60% of the soluble carbohydrates produced by hydrothermal digestion can form a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof. In some or other embodiments, at least 70% of the soluble carbohydrates produced by hydrothermal digestion can form a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof. In some or other embodiments, at least 80% of the soluble carbohydrates produced by hydrothermal digestion can form a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof. In some or other embodiments, at least 90% of the soluble carbohydrates produced by hydrothermal digestion can form a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof. In some or other embodiments, at least 95% of the soluble carbohydrates produced by hydrothermal digestion can form a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof.
[0082] In some embodiments, prior to hydrothermal digestion, cellulosic biomass solids can be washed, chemically treated and/or reduced in size (e.g., chopping, grinding, peeling and the like) to obtain a desired size and quality to be digested. In some embodiments, the above operations can remove substances that interfere with further chemical transformation of soluble carbohydrates and/or improve penetration of digestion solvent into cellulosic biomass solids. In some embodiments, washing or chemical treatment of cellulosic biomass solids may occur in the hydrothermal digestion unit before hydrothermal digestion occurs. In other embodiments, washing or chemical treatment of the cellulosic biomass solids can take place before the biomass is supplied to the hydrothermal digestion unit.
[0083] In some embodiments, the present methods may further comprise performing a phase separation of the reaction product. In various embodiments, performing a phase separation may comprise separating a bilayer, conducting a solvent removal operation, performing an extraction, performing a filtration, performing a distillation, or the like. In some embodiments, azeotropic distillation can be conducted.
[0084] In some embodiments, the methods described here may further comprise converting the reaction product into a biofuel. As used herein, the term "biofuel" will refer to any transport fuel formed from a biological source. Such biofuels may also be referred to here as "fuel blends". In some embodiments, conversion of the reaction product into a biofuel can start with a catalytic reduction reaction to transform soluble carbohydrates produced from hydrothermal digestion into a more stable reaction product, in the manner described above. In some embodiments, the reaction product may be further transformed by any number of additional catalytic reforming reactions including, for example, additional catalytic reduction reactions (eg, hydrogenolysis reactions, hydrogenation reactions, hydrotreating and the like), condensation reactions, isomerization reactions, desulfurization reactions, dehydration reactions, oligomerization reactions, alkylation reactions, and the like A description of the initial hydrogenolysis reaction and the additional catalytic reforming reactions are described below.
[0085] Several processes are known to carry out hydrogenolysis of carbohydrates. A suitable method includes bringing a stable carbohydrate or hydroxyl intermediate into contact with hydrogen, optionally mixed with a diluent gas, and a hydrogenolysis catalyst under conditions effective to form a reaction product comprising oxygenated intermediates such as, for example, smaller molecules or polyols. As used herein, the term "smaller molecules or polyols" includes any molecule that has a lower molecular weight, which may include a smaller number of carbon atoms or oxygen atoms, than the starting carbohydrate. In some embodiments, reaction products can include smaller molecules such as, for example, polyols and alcohols. This aspect of hydrogenolysis entails the breaking of carbon-carbon bonds.
[0086] In some embodiments, a soluble carbohydrate can be converted to relatively stable oxygenated intermediates such as, for example, propylene glycol, ethylene glycol and glycerol using a hydrogenolysis reaction in the presence of a catalyst that is capable of activating molecular hydrogen. Suitable catalysts may include, for example, Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os, and alloys or any combination thereof, either alone or with promoters such as Au, Ag, Cr, Zn, Mn, Sn, Bi, B, O and alloys or any combination thereof. In some embodiments, catalysts and promoters can allow hydrogenation and hydrogenolysis reactions to occur at the same time or in succession, such as the hydrogenation of a carbonyl group to form an alcohol. The catalyst may also include a carbonaceous pyropolymer catalyst containing transition metals (eg, chromium, molybdenum, tungsten, rhenium, manganese, copper and cadmium) or Group VIII metals (eg, iron, cobalt, nickel, platinum, palladium , rhodium, ruthenium, iridium and osmium). In certain embodiments, the catalyst can include any of the above metals combined with an alkaline earth metal oxide or adhered to a catalytically active support. In certain embodiments, the catalyst described in the hydrogenolysis reaction can include a catalyst support.
[0087] The conditions under which the hydrogenolysis reaction takes place will vary based on the type of biomass starting material and the desired products (eg, gasoline or diesel), for example. Persons skilled in the art, with the benefit of this disclosure, will realize the proper conditions of use to carry out the reaction. In general, the hydrogenolysis reaction can be carried out at temperatures in the range from 110°C to 300°C, and preferably from 170°C to 300°C, and above all preferably from 180°C to 290°C.
[0088] In some embodiments, the hydrogenolysis reaction may be conducted under basic conditions, preferably at a pH of 8 to 13, and even more preferably at a pH of 10 to 12. In some embodiments, the hydrogenolysis reaction may be conducted at a pressure ranging between 1 bar (absolute) (100 kPa abs) and 150 bar (15,000 kPa), and preferably at a pressure ranging between 15 bar (1,500 kPa) and 140 bar (14,000 kPa), and even more preferably at one pressure ranging from 50 bar (5,000 kPa) to 110 bar (11,000 kPa).
[0089] The hydrogen used in the hydrogenolysis reaction can include external hydrogen, recycled hydrogen, IN SITU generated hydrogen, or any combination of these.
[0090] In some embodiments, the reaction products of the hydrogenolysis reaction may comprise more than 25% by mole, or alternatively, more than 30% by mole of polyols, which can result in a greater conversion of a biofuel into a reaction of subsequent processing.
[0091] In some embodiments, hydrogenolysis can be conducted under neutral or acidic conditions, as necessary to accelerate hydrolysis reactions in addition to the hydrogenolysis reaction. For example, hydrolysis of oligomeric carbohydrates can be combined with hydrogenation to produce sugar alcohols, which can undergo hydrogenolysis.
[0092] A second aspect of hydrogenolysis involves the breaking of -OH bonds such as: RC(H)2-OH + H2 -> RCH3 + H2O. This reaction is also called "hydrodeoxygenation", and can occur in parallel with CC bond-breaking hydrogenolysis. Diols can be converted to mono-oxygenates through this reaction. As the severity of the reaction increases with increasing temperature or time of catalyst contact, the concentration of polyols and diols relative to mono-oxygenates may decrease as a result of hydrodeoxygenation. Selectivity for CC vs. C-OH bond hydrogenolysis will vary with catalyst type and formulation. occur, but is generally undesirable if the intention is to produce monooxygenates or diols and polyols that can be condensed or oligomerized to higher molecular weight compounds in a subsequent processing step. Typically, it is desirable to send only monooxygenates or diols to subsequent processing steps, as higher polyols can lead to excessive coke formation during condensation or oligomerization. to the. Alkanes, in contrast, are essentially unreactive and cannot be easily combined to produce higher molecular compounds.
[0093] Once oxygenated intermediates have been formed by a hydrogenolysis reaction, a portion of the reaction product can be recirculated to the hydrothermal digestion unit to serve as an internally generated digestion solvent. A further portion of the reaction product can be extracted and subsequently processed by further reforming reactions to form a biofuel. Before being subjected to further reforming reactions, oxygenated intermediates can optionally be separated into different components. Suitable separations can include, for example, phase separation, solvent removal columns, extractors, filters, distillations and the like. In some embodiments, a separation of lignin from oxygenated intermediates can be conducted before the reaction product is subsequently further processed or recirculated to the hydrothermal digestion unit.
[0094] Oxygenated intermediates can be processed to produce a fuel mixture in one or more processing reactions. In some embodiments, a condensation reaction can be used in conjunction with other reactions to generate a fuel mixture and can be catalyzed by a catalyst comprising an acid, a base, or both. In general, without being limited to any particular theory, it is believed that basic condensation reactions may involve a series of steps involving: (1) an optional dehydrogenation reaction; (2) an optional dehydration reaction that can be acid catalyzed; (3) an aldol condensation reaction; (4) an optional ketonization reaction; (5) an optional furan ring opening reaction; (6) hydrogenating the resulting condensation products to form a >C4 hydrocarbon; and (7) any combination of these. Acid-catalyzed condensations may similarly imply optional hydrogenation or dehydrogenation reactions, dehydration, and oligomerization reactions. Additional polishing reactions can also be used to tailor the product to a specific fuel standard, including reactions conducted in the presence of hydrogen and a hydrogenation catalyst to remove functional groups from the final fuel product. In some embodiments, a base catalyst, a catalyst having both an acidic and a base functional site, and optionally comprising a metal functional, can also be used to carry out the condensation reaction.
[0095] In some embodiments, an aldol condensation reaction can be used to produce a fuel mixture meeting the requirements for a diesel fuel or jet fuel. Traditional diesel fuels are petroleum distillates rich in paraffin hydrocarbons. They have boiling ranges as wide as 187°C to 417°C, which are suitable for combustion in a compression-ignition engine such as a diesel engine vehicle. The American Society of Testing and Materials (ASTM) sets the diesel grade according to the boiling range, along with allowable ranges of other fuel properties such as cetane number, cloud point, flash point, viscosity, point of aniline, sulfur content, water content, ash content, copper band corrosion and carbon residue. Thus, any fuel mixture that meets ASTM D975 can be defined as diesel fuel.
[0096] The present disclosure also provides methods for producing jet fuel. Jet fuel has a light straw color. The most common fuel is an unleaded/paraffin oil-based fuel classified as Airplane A-1, which is produced to an internationally standardized set of specifications. Jet fuel is a mixture of a large number of different hydrocarbons, possibly as much as a thousand or more. Their size range (molecular weights or carbon numbers) is restricted by product requirements, eg freezing point or smoke point. Kerosene-type aircraft fuel (including A-jet and A-1-jet) has a carbon number distribution between C8 and C16. Broader distillation range or naphtha-type aircraft fuel (including Jet B) typically has a carbon number distribution between C5 and C15. A fuel mixture that meets ASTM D1655 can be defined as jet fuel.
[0097] In certain embodiments, both aircraft fuels (Jet A and Jet B) contain numerous additives. Additives used include, but are not limited to, antioxidants, antistatic agents, corrosion inhibitors, and fuel system icing inhibitor (FSII) agents. Antioxidants prevent secretion and are usually based on alkylated phenols, eg AO-30, AO-31, or AO-37. Antistatic agents dissipate static electricity and prevent sparking. Stadis 450 with dinonylnaphthylsulfonic acid (DINNSA) as the active ingredient is an example. Corrosion inhibitors (eg DCI-4A) are used for civil and military fuels, and DCI-6A is used for military fuels. FSII agents include, for example, Di-EGME.
[0098] In some embodiments, oxygenated intermediates can comprise a carbonyl-containing compound that can take part in a base-catalyzed condensation reaction. In some embodiments, an optional dehydrogenation reaction can be used to increase the amount of carbonyl-containing compounds in the oxygenated intermediate stream to be used as a feed for the condensation reaction. In these embodiments, the oxygenated intermediates and/or a portion of the biological feed stock stream can be dehydrogenated in the presence of a catalyst.
[0099] In some embodiments, a dehydrogenation catalyst may be preferred for a stream of oxygenated intermediates comprising alcohols, diols and triols. In general, alcohols cannot directly participate in aldol condensation. The hydroxyl group or groups present can be converted to carbonyls (eg aldehydes, ketones, etc.) in order to participate in an aldol condensation reaction. A dehydrogenation catalyst can be included to carry out dehydrogenation of any alcohols, diols or polyols present to form ketones and aldehydes. The dehydration catalyst is typically formed from the same metals used for hydrogenation, hydrogenolysis, or to reform the aqueous phase. These catalysts are described in more detail above. Dehydrogenation yields can be increased by removing or consuming hydrogen as it forms during the reaction. The dehydrogenation step can be carried out as a separate reaction step before an aldol condensation reaction, or the dehydrogenation reaction can be carried out in combination with the aldol condensation reaction. For aldol dehydrogenation and condensation reactions in combination, the aldol dehydrogenation and condensation functions can take place on the same catalyst. For example, a metal hydrogenation/dehydrogenation functionality may be present in the catalyst comprising a basic functionality.
[00100] The dehydrogenation reaction can result in the production of a carbonyl-containing compound. Suitable carbonyl-containing compounds can include, but are not limited to, any compound comprising a carbonyl functional group that can form carbanion species or can react in a condensation reaction with a carbanion species. In one embodiment, a carbonyl-containing compound can include, but are not limited to, ketones, aldehydes, furfurals, hydroxycarboxylic acids and carboxylic acids. Ketones may include, without limitation, hydroxyketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3- dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, diketohexane, dihydroxyacetone and isomers thereof. Aldehydes may include, without limitation, hydroxyaldehydes, acetaldehyde, glyceraldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal and isomers thereof. Carboxylic acids may include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, including hydroxylated derivatives such as 2-hydroxybutanoic acid and lactic acid. Furfurals may include, without limitation, hydroxylmethylfurfural, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid, dihydro-5- (hydroxymethyl)-2(3H)-furanone, tetrahydrofururyl alcohol, 1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural and isomers thereof. In one embodiment, the dehydrogenation reaction can result in the production of a carbonyl-containing compound that is combined with oxygenated intermediates to make a part of the oxygenated intermediates fed into the condensation reaction.
[00101] In one embodiment, an acid catalyst can be used to optionally dehydrate at least a portion of the stream of oxygenated intermediates. Suitable acid catalysts for use in the dehydration reaction may include, but are not limited to, mineral acids (eg, HCl, H2SO4), solid acids (eg, zeolites, ion exchange resins) and acid salts (eg, LaCl3). Additional acid catalysts may include, without limitation, zeolites, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides, oxides of magnesium, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and any combination thereof. In some embodiments, the dehydration catalyst can also include a modifier. Suitable modifiers can include, for example, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and any combination thereof. Modifiers can be used, INTER ALIA, to carry out a hydrogenation/dehydrogenation reaction combined with the dehydration reaction. In some embodiments, the dehydration catalyst can also include a metal. Suitable metals may include, for example, Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys, and any combination of these. The dehydration catalyst can be self-supporting, supported on an inert support or resin, or it can be dissolved in solution.
[00102] In some embodiments, the dehydration reaction can occur in the vapor phase. In other embodiments, the dehydration reaction can take place in the liquid phase. For liquid phase dehydration reactions, an aqueous solution can be used to carry out the reaction. In one embodiment, solvents other than water can be used to form the aqueous solution. For example, water-soluble organic solvents can be present. Suitable solvents may include, but are not limited to, hydroxymethylfurfural (HMF), dimethylsulfoxide (DMSO), 1-methyl-n-pyrolidone (NMP), and any combination thereof. Other suitable aprotic solvents can also be used alone or in combination with any such solvent.
[00103] In one embodiment, the processing reactions may comprise an optional ketonization reaction. A ketonization reaction can increase the number of ketone functional groups on at least a portion of the oxygenated intermediates. For example, an alcohol can be converted to a ketone in a ketonization reaction. Ketonization can be carried out in the presence of a basic catalyst. Any of the basic catalysts described above as the basic component of the aldol condensation reaction can be used to carry out a ketonization reaction. Suitable reaction conditions are known to those skilled in the art and generally correspond to the reaction conditions listed above with respect to the aldol condensation reaction. The ketonization reaction can be carried out as a separate reaction step, or it can be carried out in combination with the aldol condensation reaction. The inclusion of a basic functional site on the aldol condensation catalyst can result in combined aldol condensation and ketonization reactions.
[00104] In some embodiments, the processing reactions may comprise an optional furan ring opening reaction. A furanic ring opening reaction can result in the conversion of at least a portion of any oxygenated intermediate comprising a furanic ring to compounds that are more reactive in an aldol condensation reaction. A furan ring opening reaction can be carried out in the presence of an acidic catalyst. Any of the acid catalysts described above as the acid component of the aldol condensation reaction can be used to carry out a furan ring opening reaction. Suitable reaction conditions are known to those skilled in the art and generally correspond to the reaction conditions listed above with respect to the aldol condensation reaction. The furan ring opening reaction can be carried out as a separate reaction step, or it can be carried out in combination with the aldol condensation reaction. The inclusion of an acid functional site on the aldol condensation catalyst can result in a furan ring opening reaction and joint aldol condensation reactions. Such an embodiment may be advantageous as any furan ring can be opened in the presence of an acidic functionality and reacted in an aldol condensation reaction using a basic functionality. A joint reaction scheme like this can allow the production of a greater amount of higher hydrocarbons to be formed for a given feed of oxygenated intermediates.
[00105] In some embodiments, the production of a compound >C4 can occur by condensation, which can include aldol condensation of the oxygenated intermediates in the presence of a condensation catalyst. Aldol condensation in general involves carbon-carbon coupling between two compounds, at least one of which may contain a carbonyl group, to form a larger organic molecule. For example, acetone can react with hydroxymethylfurfural to form a C9 species, which can subsequently react with another hydroxymethylfurfural molecule to form a C15 species. In various embodiments, the reaction is typically carried out in the presence of a condensation catalyst. The condensation reaction can be carried out in the vapor or liquid phase. In one embodiment, the reaction can take place at a temperature ranging from 5°C to 375°C depending on the reactivity of the carbonyl group.
[00106] The condensation catalyst in general will be a catalyst capable of forming longer chain compounds connecting two molecules through a new carbon-carbon bond, such as a base catalyst, a multifunctional catalyst with both acid and base functionalities, or any type of catalyst also comprising an optional metal functionality. In some embodiments, the multifunctional catalyst can be a catalyst with both strong acid and strong base functionalities. In some embodiments, aldol catalysts can comprise Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si, Ba, Al, Zn, Ce, La, Y, Sc, Y, Zr, Ti, hydrotalcite , zinc aluminate, phosphate, base treated aluminosilicate zeolite, a basic resin, basic nitride, alloys or any combination thereof. In some embodiments, the base catalyst may also comprise an oxide of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Co, Ni, Si, Cu, Zn, Sn , Cd, Mg, P, Fe, or any combination of these. In some embodiments, the condensation catalyst comprises base catalysts mixed with oxide. Suitable oxide mixed base catalysts may comprise a combination of magnesium, zirconium and oxygen, which may comprise without limitation: Si--Mg-O, Mg-Ti-O, Y-Mg-O, Y-Zr-O, Ti -Zr-O, Ce-Zr-O, Ce-Mg-O, Ca-Zr-O, La-Zr-O, B-Zr-O, La-Ti-O, B-Ti—O, and any combination of these. Different Mg/Zr atomic ratios or combinations of various other elements constituting the mixed oxide catalyst may be used ranging from 0.01 to 50. In some embodiments, the condensation catalyst may additionally include a metal or alloys comprising metals, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Bi, Pb, Os, alloys and combinations of these. Such metals may be preferred when a dehydrogenation reaction has to be carried out in combination with the aldol condensation reaction. In some embodiments, preferred Group IA materials may include Li, Na, K, Cs and Rb. In some embodiments, preferred Group IIA materials may include Mg, Ca, Sr, and Ba. In some embodiments, Group IIB materials may include Zn and Cd. In some embodiments, Group IIIB materials may include Y and La. Basic resins can include resins that have basic functionality. The base catalyst can be self-supporting or adhered to any of the supports further described below, including supports containing carbon, silica, alumina, zirconia, titania, vanadia, ceria, nitride, boron nitride, heteropolyacids, alloys and mixtures thereof.
[00107] In one embodiment, the condensation catalyst can be derived from the combination of MgO and Al2O3 to form a hydrotalcite material. Another preferred material contains ZnO and Al2O3 in the form of a zinc aluminate spinel. Yet another preferred material is a combination of ZnO, Al2O3 and CuO. Each of these materials may also contain an additional metal function provided by a Group VIIIB metal, such as Pd or Pt. Such metals may be preferred when a dehydrogenation reaction is to be carried out in combination with the aldol condensation reaction. In some embodiments, the base catalyst can be a metal oxide containing Cu, Ni, Zn, V, Zr, or mixtures thereof. In other embodiments, the base catalyst can be a metallic zinc aluminate containing Pt, Pd Cu, Ni, or mixtures thereof.
[00108] In some embodiments, a base-catalyzed condensation reaction can be carried out using a condensation catalyst with both an acidic and a basic functionality. The acid aldol condensation catalyst may comprise hydrotalcite, zinc aluminate, phosphate, Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr , Ti, Zn, Cr, or any combination thereof. In additional embodiments, the acid-base catalyst can also include one or more oxides from the group of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir , Ni, Si, Cu, Zn, Sn, Cd, P, and combinations thereof. In some embodiments, the acid-base catalyst may include a metal functionality provided by Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof. In some embodiments, the catalyst can additionally include Zn, Cd or phosphate. In some embodiments, the condensation catalyst can be a metal oxide containing Pd, Pt, Cu or Ni, and even more preferably an aluminate or metal zirconium oxide containing Mg and Cu, Pt, Pd or Ni. The acid-base catalyst can also include a hydroxyapatite (HAP) combined with any one or more of the above metals. The acid-base catalyst can be self-supporting or adhered to any of the supports further described below, including supports containing carbon, silica, alumina, zirconia, titania, vanadia, ceria, nitride, boron nitride, heteropolyacids, alloys and mixtures thereof.
[00109] In some embodiments, the condensation catalyst may also include zeolites and other microporous supports that contain Group IA compounds, such as Li, Na, K, Cs and Rb. Preferably, the Group IA material may be present in an amount less than that required to neutralize the acidic nature of the support. A metal function can also be provided by the addition of Group VIIIB metals, or Cu, Ga, In, Zn or Sn. In one embodiment, the condensation catalyst can be derived from combining MgO and Al2O3 to form a hydrotalcite material. Another preferred material may contain a combination of MgO and ZrO2, or a combination of ZnO and Al2O3. Each of these materials may also contain an additional metal function provided by copper or a Group VIIIB metal, such as Ni, Pd, Pt, or combinations of the foregoing.
[00110] The condensation catalyst can be self-supporting (i.e., the catalyst does not need another material to serve as a support), or it may require a separate support suitable to suspend the catalyst in the reactant stream. An exemplary support is silica, especially silica with a high surface area (greater than 100 square meters per gram), obtained by sol-gel synthesis, precipitation, or fumigation. In other embodiments, particularly where the condensation catalyst is a powder, the catalyst system may include a binder to assist in forming the catalyst into a desirable catalyst form. Applicable forming processes may include extrusion, pelletizing, oil dripping, or other known processes. Zinc oxide, alumina and a peptizing agent can also be mixed together and extruded to produce a formed material. After drying, this material can be calcined at an appropriate temperature to form the catalytically active phase. Other catalyst supports known to those skilled in the art can also be used.
[00111] In some embodiments, a dehydration catalyst, a dehydrogenation catalyst and the condensation catalyst may be present in the same reactor, since the reaction conditions to a certain extent overlap. In these embodiments, a dehydration reaction and/or a dehydrogenation reaction can take place substantially simultaneously with the condensation reaction. In some embodiments, a catalyst may comprise active sites for a dehydration reaction and/or a dehydrogenation reaction in addition to a condensation reaction. For example, a catalyst may comprise active metals for a dehydration reaction and/or a dehydrogenation reaction together with a condensation reaction at separate locations in the catalyst or as alloys. Suitable active elements may comprise any of those listed above with respect to dehydration catalyst, dehydrogenation catalyst and condensation catalyst. Alternatively, a physical mixture of dehydration, dehydrogenation and condensation catalysts can be employed. While not intending to be bound by theory, it is believed that using a condensation catalyst comprising a metal and/or acid functionality can assist in pushing the equilibrium-limited aldol condensation reaction to completion. Advantageously, this can be used to carry out multiple condensation reactions with dehydration and/or dehydrogenation of intermediates in order to form (through condensation, dehydration and/or dehydrogenation) higher molecular weight oligomers in the form desired to produce jet fuel or diesel.
[00112] The specific >C4 compounds produced in the condensation reaction may depend on a number of factors, including, without limitation, the type of oxygenated intermediates in the reactant stream, condensation temperature, condensation pressure, catalyst reactivity and flow rate. reagent stream. In general, the condensation reaction can be carried out at a temperature at which the thermodynamics of the proposed reaction is favorable. For condensed phase liquid reactions, the pressure in the reactor may be sufficient to maintain at least a portion of the reactants in the condensed liquid phase at the reactor inlet. For vapor phase reactions, the reaction can be carried out at a temperature where the vapor pressure of the oxygenates is at least 0.1 bar (10 kPa), and the thermodynamics of the reaction is favorable. The condensing temperature will vary depending on the specific oxygenated intermediates used, but may generally range between 75°C and 500°C for reactions that occur in the vapor phase, and more preferably range between 125°C and 450°C. For liquid phase reactions, the condensing temperature can range between 5°C and 475°C, and the condensing pressure can range between 0.01 bar (1 kPa) and 100 bar (10,000 kPa). Preferably, the condensing temperature can range between 15°C and 300°C, or between 15°C and 250°C.
[00113] Variation of the factors presented, as well as others, will generally result in a modification in the specific composition and yields of compounds >C4. For example, varying the temperature and/or pressure of the reactor system, or particular catalyst formulations, can result in the production of alcohols and/or ketones >C4 rather than hydrocarbons >C4. The >C4 hydrocarbon product may also contain a variety of olefins, and alkanes of various sizes (typically branched alkanes). Depending on the condensation catalyst used, the hydrocarbon product may also include aromatic and cyclic hydrocarbon compounds. The >C4 hydrocarbon product may also contain undesirably high levels of olefins, which can lead to coking or deposit formation in combustion engines, or other undesirable hydrocarbon products. In such cases, hydrocarbons can optionally be hydrogenated to reduce ketones to alcohols and hydrocarbons, while alcohols and olefinic hydrocarbons can be reduced to alkanes, thereby forming a more desirable hydrocarbon product with reduced levels of olefins, aromatics or alcohols.
[00114] Condensation reactions can be performed in any reactor of suitable design, including continuous flow, batch, semi-batch or multi-system reactors, without limitations on design, size, geometry, flow rates and the like. The reactor system may also use a fluidized catalytic bed system, a swing bed system, a fixed bed system, a moving bed system, or a combination of the foregoing. In some embodiments, two-phase (eg, liquid-liquid) and three-phase (eg, liquid-liquid-solid) reactors can be used to carry out the condensation reactions.
[00115] In a continuous flow system, the reactor system may include an optional dehydrogenation bed adapted to produce dehydrogenated oxygen intermediates, an optional dehydration bed adapted to produce dehydrated oxygen intermediates, and a condensation bed adapted to produce > compounds C4 of oxygenated intermediates. The dehydrogenation bed can be configured to receive the reactant stream and produce the desired oxygenated intermediates, which can have an increase in the amount of carbonyl-containing compounds. The dehydration bed can be configured to receive the reactant stream and produce the desired oxygenated intermediates. The condensation bed can be configured to receive the oxygenated intermediates to make contact with the condensation catalyst and produce the desired >C4 compounds. For systems with one or more finishing steps, an additional reaction bed to drive the finishing process, or processes can be included after the condensation bed.
[00116] In some embodiments, the optional dehydration reaction, the optional dehydrogenation reaction, the optional ketonization reaction, the optional ring opening reaction, and the condensation reaction catalytic beds can be positioned in the same reactor vessel or in separate reactor vessels in fluid communication with each other. Each reactor vessel preferably may include an outlet adapted to remove product stream from the reactor vessel. For systems with one or more finishing steps, the finishing reaction bed or beds can be in the same reactor vessel together with the condensing bed or in a separate reactor vessel in fluid communication with the reactor vessel with the condensing bed. condensation.
[00117] In some embodiments, the reactor system may also include additional outlets to allow removal of portions of the reactant stream to further advance or direct the reaction to the desired reaction products, and allow for the collection and recycling of by-products for use in other portions of the system. In some embodiments, the reactor system may also include additional inputs to allow the introduction of supplementary materials to further advance or direct the reaction to the desired reaction products and allow the recycling of reaction by-products for use in other reactions.
[00118] In some embodiments, the reactor system can also include elements that allow the separation of the reactant stream into different components that can find use in different reaction schemes or simply promote the desired reactions. For example, a separation unit, such as a phase separator, extractor, purifier or distillation column, can be installed before the condensation step to remove water from the reactant stream for the purpose of advancing the condensation reaction to favor production. of higher hydrocarbons. In some embodiments, a separation unit can be installed to remove specific intermediates to enable the production of a desired product stream containing hydrocarbons in a particular carbon number range, or for use as end products or in other systems or processes. The condensation reaction can produce a wide range of compounds with carbon numbers ranging from C4 to C30 or greater. Exemplary compounds may include, for example, >C4 alkanes, >C4 alkenes, >C4 cycloalkanes, >C4 cycloalkenes, aryls, fused aryls, >C4 alcohols, >C4 ketones, and mixtures thereof. Alkanes >C4 and alkenes >C4 can range from 4 to 30 carbon atoms (ie, Alkanes C4 - C30 and aAlkenes C4 - C30) and can be branched or straight chain alkenes or alkenes. Alkanes >C4 and alkenes >C4 may also include Alkanes and alkenes C7 -C14, C12 - C24 fractions, respectively, with the C7 - C14 fraction directed to jet fuel mixtures, and the C12 - C24 fraction directed to jet fuel mixtures. diesel fuel and other industrial applications. Examples of various >C4 alkanes and >C4 alkenes may include, without limitation, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3- dimethylbutane, heptane, heptene, octane, octene, 2,2,4,-trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eic, triene eic, doenoeicos tetraeicosane, tetraeicosene, and isomers thereof.
Cycloalkanes >C4 and cycloalkenes >C4 can have from 5 to 30 carbon atoms and can be unsubstituted, mono- or multi-substituted. In the case of mono- and multi-substituted compounds, the substituted group may include a branched >C3 alkyl, a straight chain >C1 alkyl, a branched >C3 alkylene, a straight chain >C1 alkylene, a >C2 alkylene of straight chain, an aryl group, or a combination of these. In one embodiment, at least one of the substituted groups can include a branched C3 - C12 alkyl, a straight chain C1 - C12 alkyl, a branched C3 - C12 alkylene, a straight chain C1 - C12 alkylene, a C2 - C12 alkylene of straight chain, an aryl group, or a combination of these. In still other embodiments, at least one of the substituted groups can include a branched C3 - C4 alkyl, a straight chain C1 - C4 alkyl, a branched C3 - C4 alkylene, a straight chain C1 - C4 alkylene, a C2 - C4 alkylene straight chain, an aryl group, or any combination thereof. Examples of desirable >C4 cycloalkanes and >C4 cycloalkenes may include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentane, methylcyclopentene, ethylcyclopentane, ethylcyclopentene, ethylcyclohexane, ethylcyclohexene, and isomers thereof.
[00120] Aryl groups contain an aromatic hydrocarbon in either unsubstituted (phenyl), mono- or multi-substituted forms. In the case of mono- and multi-substituted compounds, the substituted group may include a branched >C3 alkyl, a straight chain >C1 alkyl, a branched >C3 alkylene, a straight chain >C2 alkylene, a phenyl group, or a combination of these. In some embodiments, at least one of the substituted groups can include a branched C3 - C12 alkyl, a straight chain C1 - C12 alkyl, a branched C3 - C12 alkylene, a straight chain C2 - C12 alkylene, a phenyl group, or any combination of these. In still other embodiments, at least one of the substituted groups can include a branched C3 -C4 alkyl, a straight chain C1 -C4 alkyl, a branched C3 -C4 alkylene, a straight chain C2 - C4 alkylene, a phenyl group, or any combination of these. Examples of various aryl compounds may include, without limitation, benzene, toluene, xylene (dimethylbenzene), ethyl benzene, para-xylene, meta-xylene, ortho-xylene, and C9 aromatics.
[00121] Fused aryls contain bicyclic and polycyclic aromatic hydrocarbons, in either unsubstituted, mono-substituted or multi-substituted form. In the case of mono- and multi-substituted compounds, the substituted group may include a branched >C3 alkyl, a straight chain >C1 alkyl, a branched >C3 alkylene, a straight chain >C2 alkylene, a phenyl group, or a combination of these. In other embodiments, at least one of the substituted groups can include a branched C3 -C4 alkyl, a straight chain C1 -C4 alkyl, a branched C3 -C4 alkylene, a straight chain C2 - C4 alkylene, a phenyl group, or any combination of these. Examples of various fused aryls can include, without limitation, naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalene, indane, indene, and isomers thereof.
[00122] Moderate fractions, such as C7 - C14, can be separated for jet fuel, while heavier fractions, such as C12 - C24, can be separated for diesel use. The heavier fractions can be used as lubricants or cracked to produce additional gasoline and/or diesel fractions. Compounds >C4 may also find use as industrial chemicals, either as an intermediate or as a final product. For example, aryl toluene, xylene, ethylbenzene, para-xylene, metaxylene and orthoxylene can find use as chemical intermediates for the production of plastic and other products. However, C9 aromatics and fused aryls, such as naphthalene, anthracene, tetrahydronaphthalene, and decahydronaphthalene, may find use as solvents in industrial processes.
[00123] In some embodiments, additional processes can be used to treat the fuel mixture to remove certain components or additionally make the fuel mixture conform to a diesel or jet fuel standard. Appropriate techniques may include hydrotreating to reduce the content or remove any oxygen, sulfur or nitrogen remaining in the fuel mixture. Conditions for hydrotreating a hydrocarbon stream will be known to those skilled in the art.
[00124] In some embodiments, hydrogenation can be performed in place or after the hydrotreating process to saturate at least some olefinic bonds. In some embodiments, a hydrogenation reaction can be performed in combination with the aldol condensation reaction including a metal functional group with the aldol condensation catalyst. Such hydrogenation can be performed to bring the fuel mixture to conform to a specific fuel standard (for example, a diesel fuel standard or a jet fuel standard). The hydrogenation of the fuel mixture stream can be carried out according to known procedures, either with the continuous method or in batches. The hydrogenation reaction can be used to remove remaining carbonyl groups and/or hydroxyl groups. In such cases, any of the hydrogenation catalysts described above can be used. In general, the finishing step can be carried out at finishing temperatures ranging between 80°C and 250°C, and finishing pressures can range between 5 bar (500 kPa) and 150 bar (15,000 kPa). In some embodiments, the finishing step can be conducted in the vapor phase or liquid phase, and use external hydrogen, recycled hydrogen, or combinations thereof as necessary.
[00125] In some embodiments, isomerization can be used to treat the fuel mixture to introduce a desired degree of branching or other shape selectivity into at least some components in the fuel mixture. It can also be used to remove any impurities before the hydrocarbons come into contact with the isomerization catalyst. The isomerization step can comprise an optional removal step, wherein the fuel mixture from the oligomerization reaction can be purified by removal with water vapor or a suitable gas such as light hydrocarbon, nitrogen or hydrogen. The optional removal step can be carried out in a countercurrent manner in a unit upstream of the isomerization catalyst, where the gas and liquid come into contact with each other, or before the actual isomerization reactor in a separate removal unit using the countercurrent principle. xxx
[00126] After the optional removal step the fuel mixture can be passed into a reactive isomerization unit comprising one or more beds of catalyst. The catalyst beds in the isomerization unit can operate either co-current or counter-current. In the isomerization unit, the pressure can vary between 20 bar (2,000 kPa) to 150 bar (15,000 kPa), preferably between 20 bar (2,000 kPa) to 100 bar (10,000 kPa), the temperature varying between 195°C and 500° C, preferably between 300°C and 400°C. In the isomerization unit, any isomerization catalyst known in the art can be used. In some embodiments, suitable isomerization catalysts can contain molecular sieve and/or a Group VII metal and/or a carrier. In some embodiments, the isomerization catalyst can contain SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and Al2O3 or SiO2. Typical isomerization catalysts may include, for example, Pt/SAPO-l/Al2O3, Pt/ZSM-22/Al2O3, Pt/ZSM-23/Al2O3 and Pt/SAPO-l/SiO2.
[00127] Other factors, such as the concentration of water or undesirable oxygen intermediates, can also effect the composition and productions of compounds >C4, as well as the stability of the activity of the condensation catalyst. In such cases, the process may include a dehydration step which removes a portion of the water prior to the condensation reaction and/or the optional dehydration reaction, or a separation unit for removing undesired oxygenated intermediates. For example, a separation unit, such as a phase separator, extractor, purifier or distillation column, can be installed prior to the condensing reactor in order to remove a portion of the water from the reactant stream containing the oxygenated intermediates. A separation unit can also be installed to remove specific oxygenated intermediates to enable the production of a desired product stream containing hydrocarbons in a particular carbon range, or for use as end products or in other systems or processes.
[00128] Thus, in some embodiments, the fuel blend produced by the processes described here may be a hydrocarbon blend that meets the requirements for jet fuel (eg, conforming to ASTM D1655). In other embodiments, the product of the processes described herein may be a hydrocarbon blend comprising a fuel blend meeting the requirements for a diesel fuel (eg, conforming to ASTM D975).
[00129] In other embodiments, a fuel blend comprising gasoline hydrocarbons (i.e., a gasoline fuel) can be produced. "Gasoline hydrocarbons" refers to hydrocarbons comprising predominantly C5-9 hydrocarbons, eg C6-8 hydrocarbons, and having a boiling point range of 32°C (90°F) to 204°C (400°F) ). Gasoline hydrocarbons may include, but are not limited to, straight-running gasoline, naphtha, fluidized or thermally catalytically cracked gasoline, VB gasoline, and additive gasoline. Gasoline hydrocarbon content is determined by ASTM Method D2887.
[00130] In yet other embodiments, the >C2 olefins can be produced by catalytically reacting the oxygenated intermediates in the presence of a dehydration catalyst at a dehydration temperature and dehydration pressure to produce a reaction stream comprising the >C2 olefins. >C2 olefins can comprise straight or branched hydrocarbons containing one or more carbon-carbon double bonds. In general, >C2 olefins can contain from 2 to 8 carbon atoms, and more preferably from 3 to 5 carbon atoms. In some embodiments, olefins can comprise propylene, butylene, pentylene, isomers thereof, and mixtures of any two or more thereof. In other embodiments, the >C2 olefins can include >C4 olefins produced by catalytically reacting a portion of the >C2 olefins in an olefin isomerization catalyst.
[00131] The dehydration catalyst may comprise an element selected from the group consisting of an acidic alumina, aluminum phosphate, silica-alumina phosphate, amorphous silica-alumina aluminosilicate, zirconia, sulfated zirconia, tungsten zirconia, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphated carbon, phosphated silica, phosphated alumina, acidic resin, heteropolyacid, inorganic acid, and a combination of any two or more of these. In some embodiments, the dehydration catalyst may further comprise a modifier selected from the group consisting of Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi , and a combination of any two or more of these. In other embodiments, the dehydration catalyst may additionally comprise an oxide of an element, the element selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In , Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and a combination of any two or more of these. In yet other embodiments, the dehydration catalyst can further comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of these, and a combination of any two or more of these.
[00132] In yet other embodiments, the dehydration catalyst may comprise an aluminosilicate zeolite. In some embodiments, the dehydration catalyst can further comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of these. In some embodiments, the dehydration catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re , Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of these, and a combination of any two or more of these.
[00133] In other embodiments, the dehydration catalyst may comprise an aluminosilicate zeolite containing bifunctional pentasil ring. In some embodiments, the dehydration catalyst can further comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of these. In some embodiments, the dehydration catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re , Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of these, and a combination of any two or more of these.
[00134] The dehydration reaction can be conducted at a temperature and pressure where the thermodynamics is favorable. In general, the reaction can be carried out in the vapor phase, liquid phase, or a combination of both. In some embodiments, the dewatering temperature can range between 100°C and 500°C, and the dewatering pressure can range between 1 bar (absolute) (100 kPa abs) and 60 bar (6,000 kPa). In some embodiments, the dehydration temperature can range between 125°C and 450°C. In some embodiments, the dewatering temperature can range between 150°C and 350°C, and the dewatering pressure can range between 5 bar (500 kPa) and 50 bar (5,000 kPa). In some embodiments, the dehydration temperature can range between 175°C and 325°C.
>C6 paraffins can be produced by catalytically reacting >C2 olefins with a stream of >C4 isoparaffins in the presence of an alkylation catalyst at an alkylation temperature and alkylation pressure to produce a product stream comprising >C6 paraffins. >C4 isoparaffins can include alkanes and cycloalkanes with 4 to 7 carbon atoms, such as isobutane, isopentane, naphthenes, and larger homologues with a tertiary carbon atom (eg, 2-methylbutane and 2,4-dimethylpentane), isomers of these, and mixtures of any two or more of these. In some embodiments, the >C4 isoparaffins stream may comprise internally generated >C4 isoparaffins, external >C4 isoparaffins, recycled >C4 isoparaffins, or combinations of any two or more of these.
[00136] Paraffins >C6 may be branched paraffins, but may also include normal paraffins. In one version, >C6 paraffins may comprise an element selected from the group consisting of a branched C6-10 alkane, a branched C6 alkane, a branched C7 alkane, a branched C8 alkane, a branched C9 alkane, a branched C10 alkane, or a mixture of any two or more of these. In one version, >C6 paraffins may include, for example, dimethylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, methylpentane, 2-methylpentane, 3-methylpentane, dimethylpentane, 2,3-dimethylpentane, 2,4- dimethylpentane, methylhexane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane, dimethylhexane, or mixtures of any two or more of these.
[00137] The alkylation catalyst may comprise an element selected from the group of sulfuric acid, hydrofluoric acid, aluminum chloride, boron trifluoride, solid phosphoric acid, chlorinated alumina, acidic alumina, aluminum phosphate, silica-alumina phosphate, aluminosilicate of amorphous silica-alumina, aluminosilicate zeolite, zirconia, sulfated zirconia, tungsten zirconia, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphated carbon, phosphate silica, phosphated alumina, acidic resin, heteropolyacid, and inorganic acid of any two or more of these. The alkylation catalyst can also include a mixture of an acid mineral with a Friedel-Crafts metal halide, such as aluminum bromide, and other proton donors.
[00138] In some embodiments, the alkylation catalyst may comprise an aluminosilicate zeolite. In some embodiments, the alkylation catalyst can further comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of these. In some embodiments, the alkylation catalyst can further comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re , Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of these, and a combination of any two or more of these.
[00139] In some embodiments, the alkylation catalyst may comprise an aluminosilicate zeolite containing bifunctional pentasil ring. In some embodiments, the alkylation catalyst can further comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of these. In some embodiments, the alkylation catalyst can further comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re , Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of these, and a combination of any two or more of these. In one version, the dehydration catalyst and the alkylation catalyst can be atomically identical.
[00140] The alkylation reaction can be conducted at a temperature where thermodynamics is favorable. In general, the alkylation temperature can range between -20°C and 300°C, and the alkylation pressure can range between 1 bar (absolute) (100 kPa abs) and 80 bar (8,000 kPa). In some embodiments, the alkylation temperature can range from 100°C to 300°C. In another version, the alkylation temperature can vary between 0°C and 100°C. In still other embodiments, the alkylation temperature can range from 0°C to 50°C. In still other embodiments, the alkylation temperature can range between 70°C and 250°C, and the alkylation pressure can range between 5 bar (500 kPa) and 80 bar (8,000 kPa). In some embodiments, the alkylation catalyst can comprise a mineral acid or a strong acid. In other embodiments, the alkylation catalyst can comprise a zeolite and the alkylation temperature can be greater than 100°C.
[00141] In some embodiments, an olefinic oligomerization reaction can be conducted. The oligomerization reaction can be carried out in any suitable reactor configuration. Suitable configurations may include, but are not limited to, batch reactors, semi-batch reactors, or continuous reactor designs such as, for example, fluidized bed reactors with external regeneration vessels. Reactor designs may include, but are not limited to, tube reactors, fixed bed reactors, or any other type of reactor suitable for carrying out the oligomerization reaction. In some embodiments, a continuous oligomerization process for the production of diesel boiling range hydrocarbons and jet fuel can be carried out using an oligomerization reactor to contact an olefin feed stream comprising short chain olefins of a length of 2 to 8 carbon atoms chain with a zeolite catalyst under high temperature and pressure, in order to convert the short chain olefins into a fuel mixture in the diesel boiling range. The oligomerization reactor can be operated at relatively high pressures from 20 bar (2,000 kPa) to 100 bar (10,000 kPa), and temperatures ranging between 150 °C and 300 °C, preferably between 200 °C and 250 °C.
[00142] The resulting oligomerization stream results in a fuel mixture that can have a wide variety of products including products comprising C5 to C24 hydrocarbons. Additional processing can be used to obtain a fuel mixture that meets a desired standard. An initial separation step can be used to generate a fuel mixture with a very narrow range of carbon numbers. In some embodiments, a separation process such as a distillation process can be used to generate a fuel mixture comprising C12 to C24 hydrocarbons for further processing. The remaining hydrocarbons can be used to produce a gasoline-fuel blend, recycled to the oligomerization reactor, or used in additional processes. For example, a kerosene fraction can be derived along with the diesel fraction and can either be used as a lighting paraffin, a jet fuel blend component in conventional crude or synthetic derived jet fuels, or as a reactant (especially fraction C10 to C13) in the process to produce LAB (Linear Alkyl Benzene). The naphtha fraction, after hydroprocessing, can be routed to a thermal cracker to produce ethylene and propylene or routed to a catalytic cracker to produce ethylene, propylene and gasoline.
[00143] Additional processes can be used to treat the fuel mixture to remove certain components or additionally make the fuel mixture conform to a diesel or jet fuel standard. Appropriate techniques may include hydrotreating to remove any remaining oxygen, sulfur, or nitrogen in the fuel mixture. Hydrogenation can be carried out after the hydrotreating process to saturate at least some olefinic bonds. Such hydrogenation can be performed to bring the fuel mixture to conform to a specific fuel standard (for example, a diesel fuel standard or a jet fuel standard). The hydrogenation step of the fuel mixture stream can be carried out according to known procedures, either continuously or in batches.
[00144] To facilitate a better understanding of the present invention, the following examples are given. The following examples are not to be limited in any way or define the scope of the invention.
[00145] Unless otherwise indicated below, reactions were conducted in a Parr 5000 HASTELLOY multireactor unit containing 6 x 75 mL reactors operated in parallel at pressures up to 135 bar (13,500 kPa) and temperatures up to 275°C, stirred per magnetic stir bar. Alternate studies were conducted in 100 mL Parr 4590 reactors, with mixing by a top-driven stirring rotor, which was also capable of achieving a pressure of 135 bar (13,500 kPa) and a temperature of 275°C. Liquid chromatographic analyzes were conducted by HPLC using a Bio-Rad Aminex HPX-87H column (300 mm x 7.8 mm) at a flow rate of 0.6 ml/min of 5 mM sulfuric acid in water and an oven temperature of 30 °C. Running time was 70 minutes.
[00146] Gas chromatographic analyzes were conducted using a 60 mx 0.32 mm ID DB-5 column 1 μm thick, with 50:1 split ratio, 2 mL/min helium flow, and column oven temperature 40°C for 8 minutes, followed by a rise to 285°C at 10°C/min and a soak time of 53.5 minutes. The injector temperature was set at 250°C, and the detector temperature was set at 300°C.
[00147] Example 1: Preparation and digestion of cellulosic biomass fines. Partially digested cellulosic biomass (cellulosic biomass fines) was obtained by treating 4.217 grams of softwood chips (pine) in a hydrothermal digestion unit at 191°C using 50% 2-propanol/water as the digestion solvent, which was flowed upward at a net flow rate of 0.20 mL/min, corresponding to an estimated interstitial fluid velocity of 0.67 ft/hour. As they were formed and fluidized, the cellulosic biomass fines were removed from the packed chip bed (nominal 8 mm x 8 mm x 3 mm) by liquid overflow and collected in a riser tube. Particle size was estimated to be 10 - 100 microns using digital image analysis.
[00148] In a separate experiment, the above digestion was repeated by heating the hydrothermal digestion unit at 250°C for 7 hours using 50% solvent 2-propanol/water, buffered by means of 0.5% sodium carbonate, at an upward directed fluid flow of 0.2 mL/min. The effluent pH was 4.6. Opening of the digestion unit after the heating period revealed total digestion of the cellulosic biomass originally contained in the digestion unit with only a small portion of suspended fines remaining. Cellulosic biomass fines were again collected in the riser tube. Less than 0.5 gram of cellulosic biomass fines was collected in the riser tube, corresponding to less than 10% of the original cellulosic biomass load.
[00149] Example 2: Use of cellulosic biomass fines to filter a slurry catalyst. As a control experiment, 0.47 grams of a NiMo-on-alumina catalyst with a nominal particulate size of 7.7 µm was suspended by stirring in 20 mL of deionized water and loaded into a 12.5 x 12.5 inch x stainless steel OD tube. 0.5 inches vertical. A 40 μm in-line filter (Swagelok) was attached at the base of the tube, followed by a dosing/cut valve directly at the base of the tube. 40 psi air pressure was applied to the top of the tube. The dose/cut valve was opened to establish a drip rate through the filter of approximately 2 drops per second. The filtrate was collected using a Teledyne/Isco Retriever 500 fraction collector set to collect fractions every one minute. The fractions were collected for 7 minutes, and the amounts of catalyst solids collected from the fractions are summarized in Table 1. As initially collected, the fractions were cloudy gray, indicating catalyst suspension. After overnight gravity sedimentation, catalyst particulates deposited at the base of the vessel, of which the catalyst fraction can be determined by direct measurement of catalyst height in enlarged digital images.

[00150] The previous experiment was repeated with the addition and suspension of 0.76 gram of cellulosic biomass fines prepared as in Example 1. Unlike the control, digital analysis revealed detectable mud catalyst only in the first bottle, and the total amount of eluted catalyst particulates was only 0.02% of the total catalyst load. Fractions were collected for 9 minutes, and the amounts of catalyst solids collected from the fractions are summarized in Table 2. In this case, the samples were stained light yellow but transparent, presumably because of soluble components leached from the cellulosic biomass fines. Backwashing of the filter after disassembly allowed recovery of the filtered catalyst.
9Example 3: Digestion of cellulosic biomass in the presence of a base-loaded sludge catalyst. The lower 2.25-inch zone of a 12.5-inch x 0.5-inch (0.402-inch ID) OD digester tube was packed with 1/8-inch ceramic beads (Denstone), followed by 0.7-inch of 14 x 40 mesh filter sand. In the sand, 0.604 gram of sulphide cobalt molybdate catalyst (DC2534, Criterion Catalysts & Technologies LP) containing 1-10% cobalt oxide and molybdenum trioxide (up to 30% in weight) on crushed alumina to a particle size of less than 100 µm. The catalyst was presulfated in the manner described in US patent application publication 20100236988. The tube was then packed with 4.00 grams of southern pine wood chips having a nominal dimension of 3mm x 5mm x 5mm , thereby forming an 8.7 inch bed of chip.
[00151] The digestion unit was base filled with 50% 2-propanol/deionized water, buffered with 0.3% by weight of sodium carbonate. Addition of the digestion solvent continued until the void spaces in the chip bed were filled and a liquid layer greater than 0.5 inch above the bed was obtained. The solvent to dry wood ratio in the packed bed was less than 5.8: 1. Liquid flow was then terminated. The digestion unit was then pressurized to 70 bar (7,000 kPa) with H2, and a continuous flow of hydrogen was added through the base of the digestion unit and vented at the top at a flow rate of 95 mL/min at room temperature and standard atmospheric pressure (STP). This flow rate corresponded to a surface linear hydrogen flow velocity of 0.05 cm/sc through the digestion unit. The base entrance port was a pipe with an O.D. of nominal 3 mm (I.D. 2 mm), thereby acting as a nozzle for gas bubble formation.
[00152] The digestion unit was then heated to 190°C for 1.5 hours, followed by heating at 240°C for 3.5 hours. At the end of the experiment, 9.24 grams of liquid product were drained from the digestion unit. 7.8 grams of liquid condensed product were also collected from the overflow charged with the hydrogen sparge. Analysis of the liquid product indicated a mixture of oxygenated products (including monohydric alcohols and glycols) at 82% of the expected theoretical yield based on the amount of carbohydrate present in the initial wood load. There were no wood solids remaining at the end of the digestion period.
[00153] Example 4: Digestion of cellulosic biomass in the presence of a top loaded sludge catalyst. The experiment of Example 3 was repeated, except the 0.600 gram of catalyst was placed on top of the chip bed, not below it. The initial solvent to dry wood ratio was less than 5.5:1. After digestion, 10.1 grams of liquid product were drained from the digestion unit, and 7.28 grams of condensed liquid product were collected from the overflow. Again, no observable wood solids remained at the end of the digestion period. In contrast to loading the catalyst below the bed of chips, which produced a relatively high yield, the yield with loading of the catalyst at the top of the bed of chips produced a yield that was only 28% of the theoretical yield. LC/MS analysis of the liquid product indicated the possible presence of oligomeric by-products with a molecular weight greater than 300 and too high for detection by gas chromatography.
[00154] Example 5: Digestion of cellulosic biomass in the presence of a base-loaded sludge catalyst at a lower pressure. The experiment of Example 3 was repeated using 6.05 grams of southern pine chips and 15.4 ml of digestion solvent, added from the base, to fully cover the chip bed. In this case, the digestion unit was pressurized only to 37 bar (3,700 kPa), relative to an estimated solvent vapor pressure of 32 bar (3,200 kPa). The flow rate of aerated hydrogen was 97 mL/min, and a 50% 2-propanol in deionized water digestion solvent was co-fed from the base of the digestion unit at a flow rate of 0.05 mL/min. The digestion unit was heated at 190°C for 1.5 hours, followed by heating at 240°C for 5 hours, with hydrogen and digestion solvent flow rates maintained at the same levels. 18.53 grams of liquid product were drained from the overflow, and 8.17 grams were drained from the digestion unit at the end of the run. 5.167 grams of wood chips were required to repack the digestion unit to its previous level. This result indicated a minimum of 85% digestion under the digestion conditions. Gas chromatographic analysis indicated only 31% conversion of the desired products. Comparison of this result with Example 3 showed that higher hydrogen pressure promoted stabilization of soluble carbohydrates in the form of a higher yield.
[00155] Example 6: Digestion of cellulosic biomass in the presence of a base-loaded sludge catalyst without hydrogen flow. The experiment of Example 5 was repeated with initial pressurization with 70 bar (7,000 kPa) of hydrogen, but only maintaining digestion solvent flow through the cellulosic biomass and no hydrogen flow. At the end of the run, 17.45 grams of liquid product was drained from the overflow, and 7.4 grams of liquid product was drained from the digestion unit. 8 mL of undigested wood was also collected after the run, indicating 50% conversion. Gas chromatographic analysis indicated 27% yield of the desired reaction product in the liquid product. Again, weaker stabilization occurred when the amount of available hydrogen was reduced by terminating its flow.
[00156] Example 7: Digestion of cellulosic biomass in the absence of a sludge catalyst. The experiment of Example 3 was repeated after addition of 6.76 grams of pine chips, but without including the slurry catalyst. Although the entire wood load was digested in 6.5 hours, GC analysis indicated that only 3% of the desired reaction product formed.
[00157] Example 8: Digestion of cellulosic biomass in the presence of a base-loaded sludge catalyst at room temperature with gas and liquid flow. The experiment of Example 3 was repeated with the addition of 5.29 grams of southern pine wood chips, but the digestion unit was kept at 23.5°C for the duration of the exposure. 7,597 grams of liquid product were drained from the digestion unit at the end of the run.
[00158] Analysis of the bed of chips after removal of the liquid product indicated uniform dispersion of the catalyst throughout the height of the cellulosic biomass bed, thereby showing that the gas and liquid flow can be effective to distribute the slurry catalyst in the cellulosic biomass solids.
[00159] Example 9: Digestion of cellulosic biomass in the presence of a base-loaded sludge catalyst at room temperature with liquid flow only. The experiment of Example 8 was repeated after filling with 7.13 grams of pine chips, except that hydrogen upflow was not used and only 0.05 mL/min digestion solvent upflow was present. 1.36 grams of liquid product were drained from the overflow and 10.67 grams of liquid product were obtained from the digestion unit. Analysis of the chip bed after removal of the liquid product showed that the catalyst was only distributed in approximately the lower 20% of the chip bed, with no catalyst found distributed in the upper portions of the wood chip load.
[00160] Example 10: Determination of minimum gas velocity required for slurry catalyst fluidization. A 100 mL graduated cylinder was filled with 1 gram of alumina/NiMo 1 slurry catalyst - 25 µm nominal and 50 grams of deionized water. A fritted sprinkler stone (ACE Glass) was placed in the base of the graduated cylinder and connected to an N2 supply using 1/8-inch Teflon tubing. The N2 flow rate was varied to determine the minimum flow rate needed to completely fluidize the slurry catalyst at the top of the liquid column. The linear gas velocity corresponding to complete fluidization determined using this method was 0.037 cm/s. Hydrogen gas flow, when used in the previous examples, exceeded this minimum velocity for catalyst fluidization and suspension.
[00161] Example 11: Pulping at high loads of cellulosic biomass solids. 2.08 grams of finely ground wood pine sawdust containing 11.3% moisture was added to 25.5 grams of deionized water in a graduated cylinder. After mixing and allowing the wood to balance, 10.4 grams of water was removed by syringe from the top of the wood bed. The cylinder was then tilted to decant additional water, but only one gram of additional water was removed, yielding a final water to dry solids ratio of 8.3:1. 0.1 gram of a slurry catalyst with a particle size of 1 - 25 microns was added, and the barrel was mixed by inverting several times. Virtually no mixing of the mud catalyst with the wood was observed because of slurry formation by the finely divided wood.
[00162] Example 12: Role of biomass particulate size in digestion rate. Parallel Parr 5000 reactors were charged with 20.0 grams of 50% 2-propanol in deionized water containing 0.05 grams of sodium carbonate. 2.70 grams of soft pine wood chips containing 39% moisture were added to each reactor. In the first reactor, a single 1 inch x 1 inch x 3 mm wood chip was added. In the second reactor, the pine wood was manually trimmed into several 1/4 inch x 1/4 inch x 3 mm mini chips. In the third reactor, the pine wood was ground in a coffee grinder to a maximum size of 3 mm nominal.
[00163] All three reactors were pressurized to 51 bar (5100 kPa) with H2 and heated to 190°C for one hour before tilting to 240°C to complete a 5 hour cycle. The reactor contents were filtered through Whatman GF/F filter paper, and the paper with solids was dried in a vacuum oven overnight at 90°C. 78 wt% wood from the first reactor dissolved, and the smaller wood chips in the other two reactors gave 72 wt% dissolution, on a water-free basis. It is believed that these results are essentially the same in experimental error and that the digestion rate is not significantly impacted by wood chip size.
[00164] Therefore, the present invention is well suited to obtain the aforementioned purposes and advantages, as well as those that are inherent. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different ways, but seeming equivalent to those skilled in the art with the benefit of the teachings herein. In addition, no limitations should be made on the construction or design details shown here, other than as described in the following claims. It is, therefore, evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present invention. The invention illustratively disclosed herein may be properly practiced in the absence of any element that is not specifically disclosed herein and/or any optional element disclosed herein. Although compositions and methods are described in the terms "comprising", "containing", or "including" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" various components and steps. All previously revealed numbers and ranges may vary by a certain amount. Whenever a numeric range with a lower limit and an upper limit is revealed, any number and any included range that falls within the range is specifically revealed. In particular, it should be understood that each range of values (of the form, "from aab", or, equivalently, "from approximately aab", or, equivalently, "from approximately ab") revealed here must be as presenting each number and range encompassed in the widest range of values. Also, the terms in the claims have their normal ordinary meaning, unless otherwise explicitly and clearly defined by the applicant. Furthermore, the indefinite articles "a" or "an", as used in the claims, are defined herein to mean one or more than one of the element it introduces. If there is any conflict in the uses of a word or term in this specification, then one or more patents or other documents that may be referenced here, definitions that are consistent with this specification shall be adopted.

权利要求:
Claims (10)
[0001]
1. Method for retaining a sludge catalyst in a desired location, characterized in that it comprises: providing cellulosic biomass solids and a molecular hydrogen activating sludge catalyst in a hydrothermal digestion unit, the sludge catalyst being capable of activating molecular hydrogen and cellulosic biomass solids comprising a digestible filter aid comprising cellulosic biomass particulates capable of forming a filter cake suitable for retaining at least a portion of the slurry catalyst therein; distributing the slurry catalyst to the cellulosic biomass solids using fluid flow; heat the cellulosic biomass solids in the hydrothermal digestion unit in the presence of sludge catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; allow a portion of the liquor phase exit the hydrothermal digestion unit; forming a filter cake comprises placing the digestible filter aid in a solids retention mechanism configured to let the liquor phase pass therethrough; collecting at least a portion of the slurry catalyst in the filter cake; and, perform a first catalytic reduction reaction on the soluble carbohydrates in the hydrothermal digestion unit, thereby at least partially forming a reaction product comprising a triol, a diol, a monohydric alcohol, or any combination thereof in the digestion unit hydrothermal; wherein the first catalytic reduction reaction comprises a hydrogenolysis reaction that is conducted at a temperature in the range of 110 °C to 300 °C and at a pressure in a range between 100 kPa (1 bar) and 15,000 kPa (150 bar); wherein the slurry catalyst is delivered into the slurry catalyst in the cellulosic biomass solids using upwardly directed fluid flow.
[0002]
2. Method according to claim 1, characterized in that the digestible filter aid is mixed with the cellulosic biomass solids before the cellulosic biomass solids are supplied to the hydrothermal digestion unit.
[0003]
3. Method according to claim 2, characterized in that the digestible filter aid is formed in the hydrothermal digestion unit by heating the cellulosic biomass solids in the presence of the digestion solvent.
[0004]
4. Method according to any one of claims 1 to 3, characterized in that the solids retention mechanism is external to the hydrothermal digestion unit.
[0005]
5. Method according to any one of claims 1 to 4, characterized in that it further comprises: removing the filter cake from the solids retention mechanism; and, returning at least a portion of the slurry catalyst to the cellulosic biomass solids.
[0006]
6. Method according to any one of claims 1 to 5, characterized in that it further comprises: dissolving at least a portion of the digestible filter aid while forming fresh digestible filter aid, the fresh digestible filter aid comprising cellulosic biomass particulates with a particulate size of at most 3 mm that are formed by heating the cellulosic biomass solids in the presence of the digestion solvent.
[0007]
7. Method according to any one of claims 1 to 6, characterized in that the sludge catalyst is supplied in the hydrothermal digestion unit before the cellulosic biomass solids are supplied.
[0008]
8. Method according to any one of claims 1 to 7, characterized in that providing the digestible filter aid comprises forming the digestible filter aid in the hydrothermal digestion unit by heating the cellulosic biomass solids in the presence of the digestion solvent.
[0009]
9. Method according to claim 8, characterized in that the fresh digestible filter aid comprises cellulosic biomass particulates with a particulate size of at most 3 mm which are formed by heating the cellulosic biomass solids in the presence of the solvent of digestion.
[0010]
10. Method according to any one of claims 1 to 9, characterized in that the mud catalyst comprises a poison tolerant catalyst.

类似技术:

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同族专利:

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公开号 | 公开日

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US20140005445A1|2014-01-02|

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US9174898B2|2015-11-03|

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CA2877489A1|2014-01-03|

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CA2877489C|2021-10-26|

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CN104520500A|2015-04-15|

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BR112014032117A2|2017-06-27|

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WO2014004859A1|2014-01-03|

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AU2013284462A1|2015-02-12|

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EP2867406B1|2018-02-07|

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PL2867406T3|2018-06-29|

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AU2013284462B2|2015-11-19|

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CN104520500B|2016-08-24|

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EP2867406A1|2015-05-06|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261665727P| true| 2012-06-28|2012-06-28|

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US61/665727|2012-06-28|

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