A method for cracking a biomass feed using a catalyst

Abstract

A method of cracking a biomass feed is provided. The method includes contacting the feed with a catalyst having a water pore volume of equal to or less than about 0.8 cm3 / g, wherein the method reduces the coke production of the reaction.

Description

A METHOD FOR CRACKING A BIOMASS FEED USING A CATALYSTCROSS REFERENCE TO RELATED APPLICATION(S)

[0001] The present application claims priority to U.S. Provisional Application No. 63 / 677,737, filed on July 31, 2024, the entirety of which is incorporated in its entirety.FIELD OF THE INVENTION

[0002] Disclosed herein are methods of cracking a biomass feed. The method includes contacting a biomass feed with a catalyst having a water pore volume of equal to or less than about 0.8 cm3 / g.BACKGROUND

[0003] The need for integration of renewable feedstocks into refined products has been driven by steadily increasing demand for more carbon neutral fuels and platform chemicals. Renewable feedstocks can be derived from FOGs (fats, vegetable oils, greases) or from the conversion of lignocellulose biomass wastes such as forest or agricultural residues. While feedstocks derived from lignocellulose wastes offer the advantage of a potentially inexhaustible raw material source, they are also associated with significant challenges. For integration into refinery processes, the first step in upgrading lignocellulose waste includes liquifying the solid waste using processes such as thermal pyrolysis or hydrothermal liquefaction. The liquid product of these processes is commonly referred to as biooil or biocrude, and includes a diverse mixture of oxygenated compounds. The significant challenges come from the combination of the high oxygen content and structure of these compounds.

[0004] It is believed that the challenges can be assessed using the Effective Hydrogen Index(EHI). Using the criteria proposed by Chen et al. in "Liquid Fuel from Carbohydrates ” ChemTech, August (1986) p. 506, a feedstock should have an EHI > 1.3 to avoid excessive deactivation and to maximize conversion of renewable carbon into desired refined products. When a thermal pyrolysis or a hydrothermal liquefaction process is used, biooils will typically have an EHI of < 0.6. indicating that it is challenging to convert them to fuels and platform chemicals. That is, biooils with a low EHI have a high tendency to condense to coke instead of being transformed into the desired products. It has been found that the EHI of the biooil can be increased via hydrotreating, which will remove oxygen and introduce hydrogen into the biooil. However, this increases cost and may limit commercial feasibility.

[0005] One process that is used within many refineries is fluid catalytic cracking (FCC). The FCC process manages metal contaminants and tolerates a wide variety of feedstocks. The FCC process is routinely used to convert heavy hydrocarbon feedstocks to lighter products, such as gasoline and distillate range fractions. In FCC processes, a hydrocarbon feedstock is injected into the riser section of a FCC unit, where the feedstock is cracked into lighter, more valuable products upon contacting hot catalyst circulated to the riser-reactor from a catalyst regenerator.

[0006] Thus, there is a need for new catalysts and catalytic processes for the conversion of biomass into refined products (such as fuels and chemical intermediates) that reduces coke yield and subsequently increases yield of desired products.SUMMARY

[0007] In an embodiment, a method of cracking a feed is provided. The method may include contacting the feed with a catalyst having a water pore volume of equal to or less than about 0.8 cm3 / g, wherein the feed comprises biomass.

[0008] In some embodiments, the water pore volume may be about 0.6 cm3 / g to about 0.8 cm3 / g. In some embodiments, the water pore volume may be about 0.8 cm3 / g.

[0009] In some embodiments, the catalyst may include a zeolite. In some embodiments, the zeolite may be included in an amount of about 15% to about 25%, based on total weight of the catalyst. In some embodiments, the zeolite may be included in an amount of about 20%, based on total weight of the catalyst.

[0010] In some embodiments, the zeolite may have a BET surface area of about 100 m2 / g to about 200 m2 / g. In some embodiments, the zeolite may have a surface area of about 100 m2 / g to about 150 m2 / g.

[0011] In some embodiments, the catalyst may include a matrix. In some embodiments, the matrix surface area may be about 150 m2 / g to about 200 m2 / g. In some embodiments, the matrix may include clay, a rare earth-doped alumina, aluminosilicate (SiCh-AECh), a silica- doped alumina, ’ / -alumina, ’ -alumina. 6-alumina. 0-alumina, K-alumina, boehmite, or a combination thereof. In some embodiments, the matrix comprises gamma-alumina.

[0012] In some embodiments, the gamma-alumina may further include a rare earth element. In some embodiments, the rare earth element may include ytterbium, gadolinium, cerium, lanthanum, or a mixture of any two or more thereof. In some embodiments, the gamma-alumina may further include an alkaline earth element. In some embodiments, thealkaline earth element may include barium, calcium, magnesium, or a mixture of any two or more thereof.

[0013] In some embodiments, the matrix may include clay. In some embodiments, the clay may include a kaolin clay. In some embodiments, the kaolin clay may include metakaolin.

[0014] In some embodiments, the zeolite may include Y zeolite, ZSM-5, ZSM-20, faujasite, mordenite, zeolite beta, dealuminated silicon-enriched zeolite, or a combination thereof.

[0015] In some embodiments, the catalyst may have a BET surface area of about 20 m2 / g to about 120 m2 / g.

[0016] In some embodiments, the catalyst may include alumina, silica, a dopant or a combination thereof.

[0017] In some embodiments, the catalyst may have an average particle size of about 70 to about 95 microns.

[0018] In some embodiments, the catalyst may include silica and alumina. In some embodiments, a ratio of Si / Al may be about 1.5 to about 3.0.

[0019] In some embodiments, the catalyst may be a microspherical catalyst.

[0020] In some embodiments, the catalyst may reduce coke yield by 5%. In some embodiments of the method, coke residue may be less than about 3%. In some embodiments of the method, coke selectivity may be improv ed / reduced by about 5 wt% to about 10 wt%.

[0021] In some embodiments of the method, the method may result in a 5% reduction in coke when compared to contacting the feed with a catalyst having a water pore volume of equal to or less than about 0.8 cm3 / g.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1 illustrates the results of the coke yield of the Examples.

[0023] FIG. 2 illustrates a summary of experimental data of coke residue verse water pore volume of the Examples.Definitions:

[0024] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0025] As used herein, "a" or “an” entity refers to one or more of that entity, e.g., “a compound” refers to one or more compounds or at least one compound unless stated otherwise. As such, the terms “a” (or “an”), “one or more”, and “at least one” are used interchangeably herein.

[0026] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Additionally, as used herein, “or” means “and / or.”

[0027] As used herein, the term “about” in connection with a measured quantity, refers to the normal variations in that measured quantity, as expected by one of ordinary skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and the precision of the measuring equipment. In certain embodiments, the term “about” includes the recited number ±5%, such that “about 10” would include from 9.5 to 10.5.

[0028] Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

[0029] The use of any and all examples, or exemplar}' language (e.g., “such as”) provided herein, is intended merely to illuminate certain materials and methods and does not pose a limitation on scope. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0030] As used herein, the term ‘‘catalyst composition” refers to a composition comprising a material that promotes a chemical reaction.

[0031] As used herein, the term '‘free” or '‘substantially free” refers to a composition that comprises less than about 1 wt%, less than about 0.5 wt%, less than about 0.25 wt%, less than about 0. 1 wt%, less than about 0.05 wt%, less than about 0.01 wt%, or 0 wt% of the component.DETAILED DESCRIPTION OF THE PRESENT DISCLOSURE

[0032] The present disclosure relates to a method of treating a hydrogen deficient (EHI<1.3) biooil stream using a catalyst. The present inventors have theorized that the process used in an FCC process, can be similarly applied. That is, a combination of continuous catalyst regeneration, periodic catalyst replacement, and flexible catalyst design can be applied to treat a biomass stream. Existing FCC units can also be used to process biooils by coprocessing with gasoil. Co-feeding the biooil with the gasoil improves the upgradability through the combination of dilution and the gasoil acting as a hydrogen donor to the biooil. When cofeeding is used with existing catalyst and process technologies, the biooil content of the feed should be less than about 10%. If the amount of biooil is above about 10%, there may be a high tendency for biooil to yield coke resulting in an overall coke yield exceeding what is acceptable to maintain the unit heat balance required for the operation of the FCC unit. The present method has found a w ay to process higher levels of biooil in a feed in combination with a catalyst designed to minimize coke formation.

[0033] Some examples of biooils, also known as renewable feedstocks, are liquids derived from biogenic sources including FOGs (fats, vegetable oils, greases) and lignocellulose wastes such as forest or agricultural residues. Currently, the more hydrogen rich fats, vegetable oils and greases are being explored at the commercial scale for conversion into platform chemicals, such as aromatics (benzene, toluene, xylene) and light olefins (ethylene, propylene, butylene). However, this may lead to a competition with food production and other food resources. Thus, converting lignocellulose based wastes offers the advantage of extensive availability and less competition. Examples of such lignocellulose waste materials include agricultural wastes, such as bagasse, straw, com stover, com husks and the like. Other examples include forestry wastes, such as wood chips and saw' dust from logging operations or waste from paper and / or paper mills. Lignocellulose wastes as understood by one in the care will be largely comprised of varying content of cellulose, hemicellulose, and lignin. Thus, lignocellulose are known for having a high oxygen content and low hydrogen content. During liquefaction of biomass waste, biomass constituents decompose into a very broad mixture of oxygenated hydrocarbonsknown as biooil or biocrude. These liquids may be rich in oxygen and deficient in hy drogen making them challenging to convert to desired products in part because they have a high tendency to yield coke. The present inventors have developed a method to treat these feeds to yield less coke and convert into more of the desired products than previous methods.

[0034] By using the method as described herein, the inventors have surprisingly found a more economical and higher yield process when treating a biomass / biooil stream with a catalyst. In particular, the inventors have studied the properties of catalysts and have found that when the catalyst has a water pore volume of equal to or less than about 0.8 cm3 / g, then significantly less coke was produced. Thus, the present inventors, without being limited to a theory, believe that there is a correlation to the water pore volume of the catalyst and coke yield and / or coke residue.

[0035] As understood herein, the term ‘'water pore volume” refers to measuring the pore volume of a catalyst by titration with water as described in ASTM method D8393-21. The water pore volume is routinely used in the characterization of heterogeneous fine solid catalysts, such as those catalysts used for catalytic cracking. As understood by one of skill in the art. to measure the water pore volume, water is drawn into the material’s mesopores and macropores. When the pores accessible to water are saturated, water forms a film on the outside of the particle marking the end point. The water pore volume is then calculated as the mass of water infiltrating a mass of solid material and reported using the units of ml water per gram solid (cm3 / gm).

[0036] As further understood by one of skill in the art, water pore volume is a measure of the porosity of a catalyst particle. Lower water pore volume is associated with a denser catalyst particle. In the design of microspherical catalysts used for catalytic cracking, one skilled in the art can adjust the density of the microspherical catalyst particle by manipulating catalyst synthesis conditions such as but not limited to aggregate particle size, aggregate particle size distribution, and conditions used to form the microspherical particle. Thus, one skilled in the art can vary particle density producing catalysts characterized by a range of water pore volumes comprised of the same composition of catalyst components.

[0037] The inventors believe, without being bound to a theory, that compared to other methods for measuring catalyst pore volume, such as dodecane infiltration or mercury intrusion, water pore volume may be more effective to determine the functionally relevant porosity that governs coke formation. This may be particularly true for hydrophilic, microporous. or tortuous structures, which are often underrepresented in mercury porosimetrybecause of its non-wetting nature and pressure limitations, and may be less accessible to nonpolar liquids like dodecane.

[0038] The present inventors believe that the observed correlation between water pore volume and coke yield of the present disclosure may suggest that the internal pore structure influencing coke formation or suppression may be more effectively captured by water. Water may infiltrate interconnected and narrow pore networks, which may influence residence time, diffusion, or the extent of secondary reactions. Additionally, water’s ability’ to interact with hydrophilic catalyst surfaces, for example, those found in amorphous silica-alumina and zeolites, may better reflect the dynamic behavior of reactants and the chemical environment at active sites where coke precursors form or are mitigated. Without being limited by theory, it is believed a denser microspherical catalyst, which is characterized by a lower water pore volume, restricts accessibility’ to the active surface within the catalyst particle that is beneficial for cracking biooil. The inventors believe reduced accessibility reduces residence time within the catalyst particle that in turn suppresses secondary reactions leading to the formation of coke. In other words, a denser microspherical catalyst may reduce coke selectivity by limiting residence time, suppressing secondary reactions, and restricting access to pore environments that favor coke formation. This architectural constraint may promote more efficient cracking and reduce the likelihood of heavy intermediates condensing into coke.

[0039] In some embodiments the biomass feed may also include a gas oil. In some embodiments, the biomass feed may include biomass in an amount of at least about 5%. at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, or at least about 45%. In some embodiments, the biomass feed may include biomass in an amount of about 5% to about 90%, about 10% to about 85%, about 15% to about 80%, about 20% to about 75%, about 25% to about 70%, about 30% to about 65%, about 35% to about 60%, about 40% to about 55%, or about 45% to about 50%, based on the total feed.

[0040] Thus, the present disclosure relates to a method of cracking a feed including biooil. The method of cracking includes applying a catalyst having a water pore volume of equal to or less than about 0.8 cm3 / g, wherein the feed includes biomass. In some embodiments, the catalyst may have a water pore volume of about 0.8 cm3 / g, about 0.7 cm3 / g, about 0.6 cm3 / g, or about 0.5 cm3 / g. In an embodiment, the water pore volume of the catalyst may be about 0.6 cm3 / g to about 0.8 cm3 / g, or about 0.8 cm3 / g.

[0041] In some embodiments, the method may result in a 5% reduction in coke when compared to contacting the feed with a catalyst having a water pore volume above 0.8 cm3 / g.

[0042] In some embodiments, the catalyst may be substantially free of a zeolite. In some embodiments, the catalyst may not include a zeolite.

[0043] In some embodiments, the catalyst may include a zeolite. In some embodiments, the zeolite may be included in an amount of about 15% to about 25%, based on total weight of the catalyst. In some embodiments, the zeolite may be included in an amount of about 15%, about 18%, about 20%, about 22%. or about 25%, based on total weight of the catalyst. In some embodiments, the zeolite may be included in in amount of about 10% to about 40%. about 15% to about 35%, or about 20% to about 30%, based on total weight of the catalyst. In some embodiments, the zeolite may be included in an amount of about 20%, based on total weight of the catalyst.

[0044] In some embodiments, the catalyst may include a zeolite. In some embodiments, the zeolite may have a BET surface area of about 100 m2 / g to about 200 m2 / g. In some embodiments, the zeolite may have a surface area of about 75 m2 / g to about 250 m2 / g, about 100 m2 / g to about 225 m2 / g, about 125 m2 / g to about 200 m2 / g, or about 150 m2 / g to about 175 m2 / g. In some embodiments, the zeolite may have a surface area of about 100 m2 / g to about 150 m2 / g.

[0045] In some embodiments, the catalyst may include a matrix. In some embodiments, the matrix may have a surface area of about 150 m2 / g to about 200 m2 / g. In some embodiments, the matrix surface area may be about 50 m2 / g to about 250 m2 / g, about 100 m2 / g to about 225 m2 / g. or about 150 m2 / g to about 200 m2 / g.

[0046] In some embodiments, the matrix may include a clay, a rare earth-doped alumina, aluminosilicate (SiCh-AEOs), a silica-doped alumina, y-alumina, / -alumina. 5-alumina, 0- alumina, K-alumina, boehmite, or a combination thereof. In some embodiments, the matrix may include gamma-alumina.

[0047] In some embodiments, the gamma-alumina may further include a rare earth element. In some embodiments, the rare earth element may include ytterbium, gadolinium, cerium, lanthanum, or a mixture of any two or more thereof.

[0048] In some embodiments, the gamma-alumina may further include an alkaline earth element. In some embodiments, the alkaline earth element may include barium, calcium, magnesium, or a mixture of any two or more thereof.

[0049] In some embodiments, the matrix may include clay. In some embodiments, clay may include a kaolin clay. In some embodiments, the kaolin clay may include metakaolin clay. The clay may also be calcined.

[0050] In some embodiments, the zeolite may include Y zeolite, ZSM-5, ZSM-20, faujasite, mordenite, zeolite beta, dealuminated silicon-enriched zeolite, or a combination thereof, the zeolite may include HY, USY, dealuminated Y, RE-Y, RE-USY, ZSM-5, ZSM- AA, IM-5, MCM-68, ZSM-57, ZSM-23, CIT-5, ZDM-35, MCM-22, MCM-56, MCM-49, UZM-8, EMM-10, ITQ-2, ITQ-30, TNU-9, ZSM-22, ZSM-18, EMM-26, Zeolite T, EMC-2, offretite, beta, ITQ-13, Zeolite A, Zeolite L, MCM-35. mordenite. ZSM-12, NU-87, ECR-1, EU-1, ZSM-50, Li-A. Na-Pl. Na-P2. Chabazite. SSZ-13, SAPO-34, zeolite RHO. SSZ-35. SAPO-5, ITQ-12, Stilbite, CIT-7, ITQ-39, Linde Q, UZM-4, Natrolite, IPC-4, ZSM-48, SSZ- 61, ITQ-4, ITQ-51, Mazzite, ZSM-4, SUZ-4, SSZ-48, SSZ— 23, SAPO-11, SAPO-31, A1PO- 18, SAPO-18, SAPO-18, SAPO-41, ITQ-7, ITQ-3, SSZ-36, MCM-58, ferrierite, Y zeolite, SAPO, or a combination thereof.

[0051] In some embodiments, the zeolite may be a large pore zeolite, for example 12 membered ring zeolites including framework types FAU, CHA, MOR and the like. In some embodiments, the zeolite may be a small pore zeolite, for example 8-10 membered rings include framework types ACO, AEI, AEN, AFN, AFT. AFX, ANA, APC, APD, ATT, CDO, DDR, DFT, EAB, EDI, EPI. ERI. GIS, GOO. IHW, ITE. ITW. LEV, KFI. MER, MON. NSL OWE, PAU, PHI, RHO, TH, SAT, SAV, SIV, THO, TSC, UEI, UFL VNI, YUG, ZON, MFI, LT A, BEA and the like. Specific examples may be ZSM-11, MFI zeolite and MCM.

[0052] In some embodiments, the catalyst may further include alumina, silica, a dopant, or a combination thereof.

[0053] In some embodiments, the catalyst may have an average particle size of about 70 to about 95 microns. In some embodiments, the catalyst may have an average particle size of about 50 to about 125 microns, about 65 to about 110 microns, about 75 to about 100 microns, or about 85 microns to about 95 microns. In some embodiments, the catalyst may have an average particle size of about 60 microns, about 65 microns, about 70 microns, about 75 microns, about 80 microns, about 85 microns, about 90 microns, about 95 microns, about 100 microns, about 110 microns, or about 125 microns.

[0054] In some embodiments, the catalyst may include a zeolite. Zeolites are crystalline aluminosilicate materials comprising silicon (Si), aluminum (Al), and oxygen (O).

[0055] In some embodiments, the catalyst composition may include silica and alumina. In some embodiments, a ratio of Si / Al may be about 1.5 to about 3.0. In some embodiments, the ratio of Si / Al may be about 1.5, about 2.2, 2.5, about 2.6, about 2.7, about 2.8, about 2.9, or about 3.0.

[0056] In some embodiments, the catalyst may be a microspherical catalyst.

[0057] In some embodiments, the catalyst may reduce coke yield by about 5%. In some embodiments, the coke residue may be less than about 3%. In some embodiments, coke selectivity may be improved or reduced by about 5 wt% to about 10 wt%. In some embodiments, the method may result in a 5% reduction in coke when compared to contacting the feed with a catalyst having a water pore volume of greater than about 0.8 cm7g.

[0058] In some embodiments, the method may be performed at a temperature of about 200°C to about 650°C. about 250°C to about 600°C. about 300°C to about 550°C. about 350°C to about 500°C, or about 400°C to about 450°C. In some embodiments, the method may be performed at a temperature of about 200°C, about 225°C, about 250°C, about 275°C, about 300°C, about 325°C, about 350°C, about 375°C, about 400°C, about 425°C, about 450°C, about 475°C, about 500°C. about 525°C, about 550°C, about 575°C, about 600°C, about 625°C, or about 650°C.

[0059] In some embodiments, the method may be performed at a pressure of about 1 atm to about 20 atm, about 2 atm to about 18 atm, about 5 atm to about 15 atm, or about 7 atm to about 12 atm. In some embodiments, the method may be performed at a pressure of about 1 atm, about 2 atm, about 3 atm. about 4 atm. about 5 atm, about 8 atm, about 10 atm. about 12 atm, about 15 atm, about 18 atm, or about 20 atm.

[0060] Claims or descriptions that include “or” or “and / or” between at least one members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The disclosure includes embodiments in which more than one, or all the group members are present in, employed in, or otherwise relevant to a given product or process.

[0061] Furthermore, the disclosure encompasses all variations, combinations, and permutations in which at least one limitation, element, clause, and descriptive term from at least one of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include at least one limitation found in any other claim that is dependent on the same base claim. Where elements are presented as lists, such as, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should be understood that, in general, where the disclosure, or aspects of the disclosure, is / are referred to as comprising particular elements and / or features, embodiments of the disclosure or aspects of the disclosure consist, or consistessentially of, such elements and / or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. Where ranges are given (such as, e.g., from [X] to [Y]), endpoints (such as, e.g., [X] and [Y] in the phrase ‘'from [X] to [Y]”) are included unless otherwise indicated. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the disclosure, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0062] Those of ordinary' skill in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein. Such equivalents are intended to be encompassed by the following claims.EXAMPLES

[0063] The following examples are intended to be illustrative and are not meant in any way to limit the scope of the disclosure.

[0064] Several tests were conducted to compare a variety of catalyst to study the properties and effect on coke production in a reactor.

[0065] In particular, microspherical catalysts were prepared containing a range of compositions of crystalline zeolite and amorphous silica-alumina with varying porosity measured using water pore volume. The framework structure of the crystalline zeolite was varied to include Zeolite Y (Samples 1-8), Zeolite Beta (Samples 9 & 10), and kaolin derived amorphous silica-alumina (Samples 11 -13). The amount of crystalline Zeolite Y was varied from 0% to 43% (Samples 1-8). The kaolin derived amorphous silica-alumina was prepared with varying surface area which would proportionally change its contribution to activity for catalytic cracking. The corresponding properties are shown in Table 1.Table 1.

[0066] Each of these samples were then inserted into a method of cracking according to an embodiment of the present disclosure. Cracking tests were conducted in a semi-batch microreactor where biooil and each of the sample catalysts were loaded into a sample chamber. While flowing nitrogen, the biooil and catalyst mixture were rapidly heated to 537°C and 1 atm total pressure while continuously withdrawing cracked gaseous products. The reaction was then quenched and the solid (coke) residue remaining on the catalyst measured. The coke production was measured and is illustrated in Figure 1.

[0067] As illustrated in Figure 1 , coke yield decreases with water pore volume. Water pore volume is a measure of the meso-scale and macro-scale pore volume of the catalyst particle. Lower water pore volume is characteristic of a denser catalyst particle. The inventors, without being limited to a theory, believe a denser particle restricts accessibility within the catalyst reducing residence time for reactants that suppresses secondary reactions leading to the formation of coke. This is supported by Figure 2, which shows that the catalyst having a water pore volume below 0.8 had a coke residue of below 4%.

[0068] From these tests, to crack biomass including lignocellulose, it is believed that a water pore volume below 0.8 cm3 / g minimizes the coke yield. From the study, it was found that the performance of inert materials suggested that the pore volume influenced thermal cracking as well as catalytic cracking. This does not mean that the catalytic surface is notimportant, but that the pore volume also plays a role in influencing coke yield. The correlation with water pore volume suggested that a specific pore volume distribution may be critical, especially with larger meso-macro pores.

[0069] It has been found that coke selectivity of cracking biomass feeds is different than gas oil streams. For example, significant changes in coke selectivity for gas oil streams is about + / - .5 wt%. In contrast, significant changes in coke selectivity for biomass is about + / - 5 to 10 wf%.

Claims

What is claimed is:

1. A method of cracking a feed comprising: contacting the feed with a catalyst having a water pore volume of equal to or less than about 0.8 cm3 / g, wherein the feed comprises biomass.

2. The method of claim 1, wherein the water pore volume is about 0.6 cm3 / g to about 0.8 cm3 / g.

3. The method of claim 1, wherein the water pore volume is about 0.8 cm3 / g.

4. The method of any one of the preceding claims, wherein the catalyst comprises a zeolite.

5. The method of claim 4, wherein the zeolite is included in an amount of about 15% to about 25%, based on total weight of the catalyst.

6. The method of claim 4, wherein the zeolite is included in an amount of about 20%, based on total weight of the catalyst.

7. The method of claim 4, wherein the zeolite has a surface area of about 100 m2 / g to about 200 m2 / g.

8. The method of claim 4, wherein the zeolite has a surface area of about 100 m2 / g to about 150 m2 / g.

9. The method of any one of the preceding claims, wherein the catalyst comprises a matrix.

10. The method of claim 9, wherein the matrix surface area is about 150 m2 / g to about 200 m2 / g.

11. The method of claim 10, wherein the matrix comprises clay, a rare earth-doped alumina, aluminosilicate (SiCh-AhCh), a silica-doped alumina, y-alumina, %-alumina. 5-alumina, 0-alumina, K-alumina, boehmite, or a combination thereof.

12. The method of claim 9-11, wherein the matrix comprises gamma-alumina.

13. The method of claim 12, wherein the gamma-alumina further comprises a rare earth element.

14. The method of claim 13, wherein the rare earth element comprises ytterbium, gadolinium, cerium, lanthanum, or a mixture of any two or more thereof.

15. The method of claim 12, wherein the gamma-alumina further comprises an alkaline earth element.

16. The method of claim 14, wherein the alkaline earth element comprises barium, calcium, magnesium, or a mixture of any two or more thereof.

17. The method of claim 11, wherein the matrix comprises clay.

18. The method of claim 17, wherein the clay comprises a kaolin clay.

19. The method of claim 18, wherein the kaolin clay comprises metakaolin.

20. The method of claim 4, wherein the zeolite comprises Y zeolite, ZSM-5, ZSM-20, faujasite, mordenite, zeolite beta, dealuminated silicon-enriched zeolite, or a combination thereof.

21. The method of any one of the preceding claims, wherein the catalyst has a BET surface area of about 20 m2 / g to about 120 m2 / g.

22. The method of any one of the preceding claims, wherein the catalyst comprises alumina, silica, a dopant or a combination thereof.

23. The method of any one of the preceding claims, wherein the catalyst has an average particle size of about 70 to about 95 microns.

24. The method of any one of the preceding claims, wherein the catalyst comprises silica and alumina.

25. The method of claim 24. wherein a ratio of Si / Al is about 2.5 to about 3.0.

26. The method of any one of the preceding claims, wherein the catalyst is a microspherical catalyst.

27. The method of any one of the preceding claims, wherein coke residue is less than about 3%.

28. The method of any one of the preceding claims, wherein coke selectivity is improved / reduced by about 5 wt% to about 10 wt%.

29. The method of any one of the preceding claims, wherein the method results in a 5% reduction in coke when compared to contacting the feed with a catalyst having a water pore volume of equal to or greater than about 0.8 cm3 / g.

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