Hydrodeoxygenation of phenolic lipids and renewable hydrocarbon fuels produced therefrom

Abstract

The present invention relates to renewable hydrocarbons, and more particularly to biomass-based diesel fuels produced in a process comprising hydrodeoxygenation (HDO) of phenolic lipids. The methods may generally include combining a phenolic lipid and a hydrocarbon diluent to provide a hydrocarbon diluted phenolic lipid, and then hydrodeoxygenating the hydrocarbon diluted phenolic lipid in a reactor to provide a reactor effluent including the hydrodeoxygenated phenolic lipid. The hydrodeoxygenated phenolic lipid is separated from the reactor effluent.

Description

Technical Field

[0001] The present invention relates to renewable hydrocarbons, more particularly to renewable hydrocarbon fuels, and most particularly to biomass based diesel fuels. Background Art

[0002] This application claims priority to U.S. Provisional Application No. 63 / 377,573, filed on September 29, 2022, the entire contents of which are incorporated herein by reference.

[0003] Hydroprocessing of fatty acids / glycerides to produce renewable diesel (RD) fuels has been described in the prior art, such as U.S. Pat. Nos. 8,026,401 and 7,968,757. The RD feedstocks described in the prior art include most conventional lipids such as animal fats and vegetable oils. As described in the cited prior art and many other relevant references, RD is produced in two conversion steps. In the first step, the hydrodeoxygenation (HDO) reaction converts the fatty acid / glyceride molecules into normal paraffins in the diesel distillation range (150-380° C.). During the HDO, the glycerol backbone of the fatty acid glyceride (i.e., triglyceride or diglyceride) is converted into propane. The reaction produces water, CO and CO. 2 As the main by-product. In order to convert C16+ normal paraffin "wax" and improve the cloud point and other low temperature flow properties, the straight chain normal paraffins in the HDO product are converted into mainly methyl branched paraffins in a second step. This second step is called "catalytic dewaxing" or "hydroisomerization" (HI).

[0004] Due to its isoparaffinic composition (normal and isoparaffins, and almost no cycloparaffins or aromatics), RD has a very high cetane number, typically above 84. This makes it an excellent fuel for compression ignition engines.

[0005] However, fatty acid derived RD also has certain disadvantages. Typical RD density values ​​are about 780 kg / m 3 , which is lower than petroleum diesel (usually about 880kg / m 3 ) and biodiesel (about 850kg / m 3 ). Because higher mass density generally translates to higher energy density, a higher density hydrocarbon composition is desirable for renewable diesel.

[0006] Co-hydrogenation of conventional lipids with petroleum fractions has been disclosed in the prior art. For example, Jerzy Walendziewski and colleagues have described the co-hydrogenation of 10% and 20% rapeseed oil with straight-run diesel / light gas oil (Fuel Processing Technology 90, 2009, 686-691). In a more recent study, P. Dhar and colleagues reported the co-processing of 5-15% palm oil and jatropha oil with straight-run gas oil (Hydrocarbon Processing, January 2018; 25-28). These studies broadly describe the chemical conversion of lipids with primarily C16 and C18 fatty acids to n-paraffins in the C15-C18 range, and emphasize that the low-temperature properties (i.e., cloud point, CFPP, pour point) of the treated diesel deteriorate with increasing feed lipid content. In addition, refineries that target co-hydrogenation are generally not equipped to handle carbonic acid corrosion (caused by water and CO previously described herein). 2 Co-hydrogenation of conventional lipids with petroleum fractions has also been shown to affect the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) activities of the catalyst, as described by Rasmus Egeberg and colleagues (Petroleum Technology Quarterly, Part 2, 2010, 1-11, and Top Catal (2009) 52:229-240) and Jane Yao et al. (US8932453). Specifically, the CO byproduct has been shown to inhibit the activity of the catalyst, particularly the cobalt-molybdenum (CoMo) hydroprocessing catalyst commonly used in petroleum refining, for HDS, HDN and HDA reactions. CO inhibition of nickel-molybdenum (NiMo) catalysts is less pronounced. As a result of the inhibition, in order to achieve sulfur specifications in the product, the co-processing operation must be carried out at higher reactor temperatures, which results in a possible shortening of the catalyst service life.

[0007] Due to the paraffinic nature of fatty acid HDO products, they have high cloud points (typically 20 to 22°C) and require a high degree of isomerization to reduce the cloud point value by 20-40°C for use as a neat fuel. The main HDO product of a typical fatty acid lipid is n-octadecane (C18 n-paraffin), which has a melting point of 28°C. In comparison, n-dodecylcyclohexane (C18 alkylcyclohexane) has a melting point of 9°C. Alkyl aromatic compounds have even lower melting points, with n-dodecylbenzene (C18 alkylbenzene) reported to have a melting point of -7°C.

[0008] Another disadvantage of the RD process based on fatty acid glyceride feedstock relates to the expense and capital cost of the equipment. Separation and recovery of the propane by-product adds a number of processing units and equipment to the facility that are not directly related to the manufacture of RD.

[0009] Another process disadvantage is related to the oxygen content of the feedstock. When the fatty acid feedstock has more than 11% by weight of oxygen, a large amount of hydrogen is used to remove the oxygen as a water effluent. In addition, fatty acid deoxygenation always leads to the formation of carbon oxides (CO and CO 2 ) and water, which requires equipment to separate these non-condensable gaseous by-products from the recycled hydrogen.

[0010] One class of biomass-based liquid feedstocks that potentially addresses some of these deficiencies is phenolic bio-oils. As those skilled in the art will recognize, phenols undergo hydrodeoxygenation to produce aromatics (e.g., benzene; 876 kg / m 3 ) and cycloalkanes (e.g., cyclohexane; 779 kg / m 3 ), whose energy density is greater than that of normal paraffins with equivalent carbon numbers (e.g., normal hexane; 655 kg / m 3 ) or isoparaffin (e.g., 2-methylpentane; 653 kg / m 3 The prior art has disclosed the production of phenolic bio-oils from lignocellulosic biomass. However, the prior art also highlights the challenges of processing such phenolic bio-oils, including incomplete deoxygenation and relatively rapid catalyst deactivation.

[0011] Therefore, there is an unmet need for a renewable diesel with higher energy density and lower capital cost process.

[0012] Applicants have identified a class of lipids that address the aforementioned needs. Such lipids are referred to as phenolic lipids. These phenolic lipids are structurally similar to conventional non-phenolic fatty acid lipids, but have the aforementioned advantages provided by the phenolic functionality. The similarities and differences between conventional fatty acid lipids and phenolic lipids can be observed through the schematic molecular structures I and II of stearic acid and anacardic acid, respectively.

[0013]

[0014] Thus, structure II represents a lipid having fused phenol groups attached to the second and third carbons from the carboxylic acid carbon of the fatty acid molecule.

[0015] Thus, phenolic lipids have a carboxylic acid group in the ortho position to the phenol and an alkyl / alkenyl chain in the meta position. Phenolic lipids also include structures such as catechol (1,2-dihydroxybenzene) in place of phenol (hydroxybenzene).

[0016] The prior art discloses that carboxylic acid groups can be removed by thermal treatment, including pyrolysis, mechanical processing, and distillation, to provide thermally decarboxylated phenolic lipids. Removal of carboxylic acid groups provides the additional benefit of reducing or eliminating CO byproduct production during HDO. This effect can be particularly beneficial for co-processing with petroleum feedstocks, where inhibition of HDS activity by CO can be reduced and inclusion of more renewable feedstocks can be achieved.

[0017] Conventional lipids are susceptible to oxidation. Auto-oxidation is carried out by atmospheric oxygen, wherein the process begins by a free radical reaction involving unsaturated fatty acids. The main product formed is hydroperoxide, which then decomposes in a series of complex reactions to form many secondary products. These secondary products may include alcohols and carbonyl compounds, as well as polymers / oligomers. U.S. Patent No. 2,482,760 describes a method for separating oleic acid and polyunsaturated fatty acids (having similar boiling temperatures) by thermally polymerizing the latter. U.S. Patent No. 2,664,429 discloses an alternative method for thermally polymerized fatty acids. Thermally polymerized unsaturated fatty acid esters (e.g., Paschke, RF; Wheeler, DH; The Journal of the American Oil Chemists' Society, June 1949; Pages 278-283) are also disclosed in the prior art. The oxidative stability of fats and oils is measured using an active oxygen method (AOCS Cd 12-57) or a Rancimat method (AOCS Cd 12b-92).

[0018] Prior art teaches that alkylphenols are effective antioxidants. Hindered phenols such as butyrated hydroxytoluene (BHT) are versatile antioxidants used in a variety of products, including fuels and oils. Similar compounds (e.g., hydroquinone) have also been used commercially as short inhibitors to inhibit polymerization reactions (see, e.g., Index of Commercial Antioxidants and Antiozonants; The Goodyear Tire & Rubber Co.; 1999). Summary of the invention

[0019] In one aspect of the invention, the density (at 15.6°C) is 780 kg / m 3 A renewable diesel fuel having an NH40-60% carbonyl group and a cloud point of 18° C. or less is produced in a process comprising hydrodeoxygenating (HDO) the phenolic lipids. In embodiments, the phenolic lipids are decarboxylated prior to HDO conversion.

[0020] In different aspects of the invention, the phenolic lipid HDO process uses green hydrogen from water electrolysis. In some embodiments, the phenolic lipids are pre-hydrogenated. In other embodiments, the pre-hydrogenated phenolic lipids are used as carriers of green hydrogen. In still other embodiments, the pre-hydrogenated phenolic lipids are subjected to the HDO process to produce renewable diesel. In other embodiments, the pre-hydrogenated phenolic lipids are blended with conventional non-phenolic fatty acid lipids before HDO is converted into renewable diesel. In some embodiments, the RD converted from HDO is hydroisomerized to further reduce the cloud point. In other embodiments, the RD converted from HDO is hydrocracking into renewable jet fuel or sustainable aviation fuel (SAF) and renewable gasoline.

[0021] In embodiments, phenolic lipids are used to provide antioxidant and anti-polymerization properties to conventional fatty acid-based lipids. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 An exemplary reaction scheme for the conversion of phenolic lipids to hydrocarbon fuel components is depicted;

[0023] Figure 2 is a process flow diagram illustrating an embodiment of a method for producing renewable diesel from phenolic lipids;

[0024] Figure 3 is a process flow diagram illustrating an embodiment of a method for converting phenolic lipids in a batch reactor;

[0025] Figure 4 is a chromatogram from a gas chromatography-mass spectrometry (GCMS) instrument showing product peaks associated with Example 2; and

[0026] Figure 5 is a graph showing the results of an oxidation stability test related to Example 3. DETAILED DESCRIPTION

[0027] Decarboxylation of phenolic lipids: Phenolic lipids (PL) are readily decarboxylated using heat treatment to provide decarboxylated phenolic lipids (DPL). Figure 1 An exemplary conversion route is provided in which the typical PL compound anacardic acid is decarboxylated to the corresponding DPL cardanol. Any number of conditions and equipment (which provide heating the PL to a temperature of 250-550°F, usually in the absence of air (to avoid oxidation)) can be used to achieve the conversion of PL to DPL. The decarboxylation system and equipment include a stirred reactor with a heating jacket for heating with steam or hot oil. Alternatively, a container with steam injection can be used. Alternatively, reactive distillation can be used. As recognized by those skilled in the art, many variations exist and can be used to optimize the decarboxylation reaction.

[0028] Hydrogenation of phenolic lipids: DPLs are hydrogenated by saturating the carbon-carbon double bonds in the benzene ring and the alkyl group. In the case of cardanol, the alkyl group is a 15 carbon chain with 1, 2 or 3 carbon-carbon double bonds. Figure 1 As shown, the hydrogenated phenol lipid (HPL) can be an alkyl cyclohexanone or an alkyl cyclohexanol, depending on the degree of functional group reduction. Hydrogenation is often carried out at a relatively high pressure (100 to 2000 psig) at a temperature of 250 to 500 ° F. Preferred catalysts include palladium on alumina, or reduced nickel or sponge metal catalysts (e.g., RANEY catalysts) on the same carrier. DPL can be hydrogenated in both batch or continuous reactors, using fixed bed or slurry catalyst reactor systems.

[0029] Hydrodeoxygenation of phenolic lipids: HPL compounds can be Figure 1 Equations 3a and 3b are subjected to HDO to hydrocarbons. For the hydrodeoxygenation of phenolic lipids, sulfided molybdenum or tungsten catalysts with hydrogenolysis activity are preferred. Promoters for HDO catalysts include nickel and cobalt. In the present invention, reactor conditions are selected so that PL can be converted to RD in one step (combining equations 1, 2a, 2b, 3a and 3b). At 100-2500 psia H 2 The HDO temperature of the present invention is 500 to 700°F at partial pressure. In an embodiment, DPL is used as the HDO feed. In an embodiment, the hydrodeoxygenation of PL / DPL to RD is carried out in one reactor, wherein the oxygen content of RD is less than 0.1 wt%, aromatics is less than 4% and the bromine index is greater than 70.

[0030] First embodiment of the present invention

[0031] See also Figure 2 In the depicted method embodiment, a biological raw material 101 containing phenolic lipids is introduced into a buffer tank 10. The phenolic lipids can be plant, bacterial, fungal, or a combination thereof. In an exemplary embodiment, the phenolic lipid is cashew nut shell liquid (CNSL). CNSL is a component of the nut of the cashew tree fruit. It is a dark reddish brown liquid enclosed in the soft honeycomb shell of the nut, which is released when the shell is broken. CNSL represents a by-product of the cashew industry. In some embodiments, the phenolic lipids include anacardic acid, cardanol, cardanol, and 2-methyl cardanol.

[0032] In other embodiments, biological feedstock 101 includes decarboxylated phenolic lipids. In embodiments, feedstock 101 may be decarboxylated CNSL (also referred to as double boiled CNSL or industrial CNSL). In embodiments, the decarboxylated phenolic lipid is at least 50% by weight cardanol.

[0033] In some embodiments, feedstock 101 is pretreated according to lipid pretreatment methods described in the prior art (e.g., U.S. Pat. Nos. 11,118,133 and 9,404,064, which are incorporated herein by reference). The purpose of pretreatment is to remove phosphorus, silicon, and metal contaminants in feedstock 101. The need for pretreatment is more important when phenolic lipids have not yet been decarboxylated, because these phenolic lipids generally have higher concentrations of such contaminants.

[0034] In embodiments where the phenolic lipids are not decarboxylated, measures may need to be taken in the buffer tank 10 to ensure that a uniform biomass is maintained. These measures include mechanical agitation or recirculation pumps, which are well known to those skilled in the art. Additional measures may include stabilizing additives such as inhibitors, surfactants, peroxide scavengers, and antioxidants.

[0035] The buffer tank 10 provides a pumped liquid 102 for pressurization and transfer as a pressurized feedstock 103. The pressurized feedstock 103 is optionally mixed with a hydrocarbon diluent such as Figure 2 The hydrocarbon product recycle stream 113 is shown combined. The hydrocarbon diluted feedstock 103A is combined with pressurized hydrogen 133 to provide a heat exchanger inlet feedstock 104. The heat exchanger inlet feedstock 104 is heated by the feed-effluent exchanger 30 to provide a heat exchanger outlet feedstock 105. The heat exchanger outlet feedstock 105 is further heated in the heater 46 to provide a heated reactor feed 106.

[0036] Heater 46 is preferably a shell and tube exchanger, wherein the reactor feed flows through the tube, and the heat transfer fluid flows through the shell side. The temperature of the heated reactor feed 106 is 500 to 700 ° F. In an embodiment, the temperature of the heated reactor feed is 520 ° F, 540 ° F, 560 ° F, 580 ° F, 600 ° F, 620 ° F, 640 ° F, 660 ° F, 680 ° F or a value between any two of these temperatures. For example, in a preferred embodiment, the heated reactor feed is 560 to 660 ° F. Although a shell and tube heat exchanger is described in this embodiment of the method, it is known to those skilled in the art that other types of heat exchangers or heating methods can also be used as recognized by those skilled in the art. For example, in a preferred embodiment, the hydrocarbon product recycle stream 113 can be heated to a certain temperature in a flame heater, which achieves the reactor feed temperature of heating described herein when combined with the pressurized raw material 103, thereby avoiding heating the phenolic lipid component in a heat exchanger.

[0037] Back to Figure 2, the heated reactor feed 106 enters a hydrodeoxygenation (HDO) reactor 20 containing a fixed bed catalyst. The HDO reactor 20 is maintained at a pressure of 500 to 2700 psig. In embodiments, the reactor is maintained at 600 psig, 800 psig, 1000 psig, 1200 psig, 1400 psig, 1600 psig, 1800 psig, 2000 psig, 2200 psig, 2400 psig, 2600 psig, or a value between any two of these pressures. In a preferred embodiment, the HDO reactor 20 is maintained at 1600 to 2400 psig.

[0038] The pressurized raw material 103 is heated for 0.3 to 6.0 hours. -1 The liquid hourly space velocity (LHSV) (vol / h feedstock 103 / vol catalyst) of 100% is introduced into the reactor. The ratio of pressurized hydrogen 133 to feedstock 103 is 2000 SCF / Bbl to 10000 SCF / Bbl. In a preferred embodiment, the reactor is operated at an LHSV value of 0.5 to 5.0 h -1 and oil:gas ratios of 4000 to 8000 SCF / Bbl.

[0039] The HDO reactor 20 includes at least one sulfided catalyst bed comprising molybdenum or tungsten. Preferred catalysts also include a nickel or cobalt promoter. These catalysts include sulfided nickel-molybdenum (NiMo), nickel-tungsten (NiW), or cobalt-molybdenum (CoMo) on an alumina or silica-alumina support. It will be appreciated by those skilled in the art that any catalyst or combination of catalysts may be used in the present invention, as long as the catalyst system functions as described herein in accordance with the present invention.

[0040] In order to maintain the functionality of the active metal sulfide of the catalyst, even though organic sulfur is absent or in very low concentrations (<40 wppm) in most biomass feedstocks, the combined feedstock 103 can be supplemented with a sulfur compound that decomposes into hydrogen sulfide when heated and / or in contact with the catalyst. Two preferred sulfur compounds are dimethyl disulfide and carbon disulfide. Their preferred concentrations in the pressurized feedstock 103 are from about 100 to about 2000 ppm by weight of sulfur.

[0041] The HDO reactor 20 operates at a weight average bed temperature (WABT) of 550 to about 650° F. In fixed bed, adiabatic reactors, WABT is often used to denote the "average" or "equivalent isothermal temperature" of the reactor, accounting for the non-linear temperature distribution between the reactor inlet and outlet according to the following equation.

[0042]

[0043] In the equation, i represents the bed number, and Wci is the weight fraction of the total catalyst in bed i. Figure 2 In the embodiment of FIG. 1 , HDO reactor 20 comprises two beds: bed 22A and bed 22B. If bed 22A and bed 22B have the same weight of catalyst and the inlet temperature is 560° F. and the outlet temperature is 640° F. (due to the adiabatic temperature rise caused by the exothermic reaction in the HDO reactor), they will each have a WABT of 1 =WABT 2 = [550°F + 2 (640°F)] / 3 = 610°F, and total WABT = 0.5 (610°F) + 0.5 (610°F) = 610°F. Figure 1 In the embodiment, quench hydrogen 107 (which is preferably a slip stream from compressed hydrogen 133) is introduced between the two reactors to reduce the inlet temperature of bed 22B. HDO reactor 20 operates with a WABT value of 580 to 640°F. In embodiments, the WABT is 580°F, 590°F, 600°F, 610°F, 620°F, 630°F, 640°F, or a range maintained between any two of these temperatures. In a preferred embodiment, the WABT is maintained at 590 to 630°F. It has been surprisingly observed that this temperature range achieves a desired balance between high phenolic oxygen removal and moderate saturation, maintaining a low cloud point, compared to fully saturated hydrocarbons.

[0044] Reactor effluent 108 is cooled by feed-effluent exchanger 30 to provide partially cooled reactor effluent 109, which is further cooled in reactor effluent cooler 32. The cooled reactor effluent 110 is at a temperature of about 250 to about 400 ° F and has liquid and vapor phase HDO products and unconverted hydrogen. The gas / gas phase 115 is separated from the liquid hydrocarbon phase 114 in separator 34. High-pressure separator 34 operates at the reactor outlet pressure (minus the pressure drop along the tube run and the exchanger). The gas / gas phase 115 includes hydrogen and water vapor byproducts of the HDO reaction. These are cooled in condenser 36 to provide a two-phase fluid that is separated in cold separator tank 38. In an embodiment, wash water 118 is introduced upstream of condenser 36 to wash any solid deposits (which may form on the condensing surface). Condensed water 117 is thereby removed from the gas phase 130 (which is primarily hydrogen). The gas phase 130 is mostly recycled through the hydrogen compressor 44. In order to maintain the purity of the pressurized hydrogen 133 at the target hydrogen purity of 80 to 99 mol% concentration, a portion of the recycle gas 130 is purged as bleed gas 130A while providing make-up hydrogen 131 to make up for chemical hydrogen consumption (as well as solubility and other losses) and maintain the gasoline: oil ratio previously described herein. In embodiments where the phenolic lipids are not decarboxylated, decarboxylation occurs in the HDO reactor and therefore more gas (comprising CO) needs to be purged. 2 and CO contaminants) as purged as bleed gas 130A. When the phenolic lipids in the bio-feedstock 101 are substantially decarboxylated (e.g., when the second boiled CNSL is phenolic lipids), a significantly lower portion (typically less than 2% of the total pressurized hydrogen 133) of the recycle gas needs to be purged as bleed gas 130A. In some embodiments using decarboxylated phenolic lipids, the bleed gas 130A is 0% to 1% of the total pressurized hydrogen 133 during normal operating conditions.

[0045] Returning to separator 34, liquid hydrocarbon phase 114 is optionally transferred to a stripper (not shown) where dissolved gas phase byproducts such as H 2 S and water to provide a hydrocarbon suitable for use as a diesel fuel or diesel fuel blending stock in a compression ignition engine. The hydrocarbon fuel composition mainly comprises alkylcyclohexanes and methylalkylcyclohexanes, wherein the alkyl group is a C9-C21 straight chain hydrocarbon. The hydrocarbon composition includes less than 0.1 wt % oxygen and up to 4 wt % aromatics. The density (at 15.5° C.) of the hydrocarbon composition is at least 780 kg / m 3 And the cloud point is 18°C ​​or lower, preferably 16°C or lower, and the bromine index is 70 or higher.

[0046] In an embodiment, the liquid hydrocarbon phase 114 is directed to another hydroprocessing reactor (not shown) where the hydrocarbons undergo hydrocracking and isomerization reactions. In some embodiments, the hydrocracking / isomerization products are fractionated to provide low cloud point diesel having a cloud point value of -5°C or less, and / or a jet fuel having a freezing point of -40°C or less.

[0047] Second embodiment of the present invention

[0048] from Figure 1 According to equations 2(a) / 2(b) and 3(a) / 3(b), the phenolic lipid hydrogenation / hydrodeoxygenation fuel composition of the present invention can advantageously produce propane, CO / CO 2 and other non-condensable gas phase byproducts. Therefore, the reaction can be carried out without gas cleaning and recycle conditions, including in a batch reactor system. Also from Equations 2(a) / 2(b) and 3(a) / 3(b), it is observed that the conversion reaction of the typical phenolic lipid molecule cardanol to hydrocarbon fuel consumes 7 mol of hydrogen (14.1 g) per mole of n-pentadecylcyclohexane product (294.6 g). If hydrogen is to be provided by intermittent renewable energy (via water electrolysis), then this technology will represent an effective method of "storing" and "carrying" renewable electricity for use as a transportation fuel, as described below.

[0049] See also Figure 3 The water electrolysis unit 50 is equipped with an anode and a cathode separated by a membrane (not shown), as described in the prior art. The water electrolysis unit or electrolyzer is supplied with water 201 and direct current 202 to convert water molecules into hydrogen 204 (from the cathode) and oxygen 203 (at the anode). Typically, 10-20 kg of H2O2 is produced per MW of electrical energy. 2 . In an embodiment, electrical energy 202 is provided by a photovoltaic power plant. In other embodiments, electrical energy 202 is provided by a wind turbine and an inverter. The electrolyzer 50 is equipped with a compressor (not shown) to increase the hydrogen pressure from close to atmospheric pressure to 100 psig or greater. In an embodiment, hydrogen 204 is supplied at a pressure of 100 to 2000 psig. In an embodiment, the compressor is a multi-stage compressor. Because electrical energy 202 is obtained intermittently (e.g., during the daylight period used in photovoltaic power plant embodiments), hydrogen 204 is not continuously available. When available, the supply valve 52 is opened to the intermittent reactor 60, which has been pre-loaded with phenolic lipid raw materials through pipeline 205. Hydrogen is dispersed into the pre-loaded feed by hydrogen injector 204A.

[0050] The batch reactor 60 is a pressure vessel designed to carry out hydrogenation reactions, preferably in slurry mode, using the same type of catalyst as described above for continuous fixed bed HDO reactor embodiments. The preferred catalyst size for batch slurry reactions is relatively small, typically with an equivalent particle size of 1.3 mm or less. The reactor is preferably equipped with an agitator system 62 to suspend the catalyst and disperse hydrogen in the pre-loaded raw materials. The batch reactor 60 also includes a device for heating and cooling via a heat transfer fluid circulating through the heating / cooling coil 206. In some embodiments, heating is provided by a reactor jacket (not shown), and cooling is provided by a cooling coil. Other reactor systems can be used for the batch reactor 60, as those skilled in the art will readily appreciate and disclosed in the prior art literature on hydrogenation equipment. These include Buss Loop reactors and hollow shaft gas supply agitator reactors. In the Buss Loop reactor, a recirculation pump and an external heat exchanger are provided with nozzles to achieve close mixing of gas / liquid / catalyst without the use of a mechanical agitator. In a hollow shaft gas-fed agitator reactor, hydrogen is dispersed into the reactor via the agitator itself.

[0051] In an embodiment, the pre-charge feed in the batch reactor 60 is decarboxylated CNSL. The catalyst may be added to the pre-charge reactor as a slurry in oil or water through line 215. In a preferred embodiment, the catalyst is a presulfided NiMo catalyst in C10-C20 hydrocarbons. The catalyst concentration in the pre-charge feed is 1 to 20 wt%, preferably 2 to 10 wt%.

[0052] The reactor is equipped with means for temperature indication / control 54 (e.g., via heat transfer fluid 206) and pressure indication / control 56 (via hydrogen supply valve 52 and back pressure control valve 72). In this manner, the reactor is maintained at a pressure of 500 to 2000 psig and a temperature of 500 to 650° F. In a preferred embodiment, the reactor is operated at a pressure of 500-1000 psi and 580-640° F.

[0053] As the phenolic lipids undergo hydrogenation and hydrodeoxygenation, hydrogen is consumed and additional hydrogen is provided to maintain pressure through hydrogen supply valve 52. At the same time, water vapor in the reactor headspace vapor 208 is condensed in condenser 68, and water byproduct is collected in condenser tank 70.

[0054] Condensed water 214 collects in condenser tank 70 during intermittent reaction cycles. In embodiments, water 214 is used to provide some of the water supplied to electrolytic cell 50.

[0055] When almost no more hydrogen is consumed (reactor pressure does not change), the reaction is complete. At this point, turn off the agitator system 62 and allow the catalyst to settle to the bottom of the reactor. Then, open valve 67 and discharge the clarified liquid product layer through pipeline 209, which leads to a fine filter (not shown) to remove any suspended catalyst and catalyst fines. The filtered hydrocarbon product mainly includes alkyl cyclohexanes and methyl alkyl cyclohexanes, and the alkyl group is a C9-C21 straight chain hydrocarbon. The hydrocarbon composition includes less than 0.1% by weight of oxygen and up to 4% by weight of aromatics. The density of the hydrocarbon composition (at 15.5°C) is at least 780kg / m 3 And the cloud point is 18°C ​​or lower, preferably 16°C or lower, and the bromine index is 70 or higher.

[0056] After product discharge, a fresh load of decarboxylated phenolic lipid feed can be loaded into reactor 60 to prepare for the next use of electrolyzer 50 (e.g., power generation from a photovoltaic solar power plant the next morning). Depending on the feed contaminants, it may be necessary to periodically discharge the spent catalyst slurry 207 completely via drain valve 69 for regeneration or disposal.

[0057] The hydrocarbon product can be used as a carbon neutral diesel or diesel fuel blendstock (having phenolic lipid carbon and hydrogen formed naturally by photosynthesis, and the hydrodeoxygenation reaction is carried out using renewable energy). This exemplary embodiment also provides a solution to the challenge of baseload electrical energy storage.

[0058] Third embodiment of the present invention

[0059] In this exemplary embodiment, a conventional lipid feedstock is blended with 0.5 to 10 wt % of phenolic lipids prior to hydrodeoxygenation.

[0060] In an embodiment, blending is performed during the transfer of the raw materials to the blending raw material storage tank. Phenolic lipids provide improved oxidative stability for conventional lipids. As a result, phenolic lipids minimize secondary reactions due to the formation of hydroperoxides, thereby improving processability (e.g., reducing corrosion due to the formation and evaporation of light carboxylic acids, and reducing scaling due to thermal polymerization). Because volatile carboxylic acids such as formic acid and acetic acid are byproducts of fatty acid oxidation, tank tops containing conventional fatty acid-based lipids tend to corrode, producing iron and other corrosion products to contaminate tank contents. The disclosed embodiments of the invention reduce such corrosion and contamination of conventional lipid raw materials.

[0061] The test method for quantifying the oxidative stability of conventional lipids is the Rancimat technology (the basis of the oxidative stability index measured according to AOCS Cd lb-92). In this test method, lipids are heated to a temperature of 80-160°C, and accelerated oxidation is carried out via air injection. The air leaving the sample is sent to a deionized water container, where the conductivity is continuously measured. The volatile organic acid by-products formed during oxidation are dissolved in water, and cause the conductivity to increase, thus marking the beginning of oxidation. The time used before the observed oxidation is called the induction time, and is typically 1 hour to 20 hours, depending on the lipid type and the test temperature. The shorter the induction time, the easier the lipid is to oxidize.

[0062] In embodiments, the blended raw material has about 1% by weight of phenolic lipids and 99% by weight of conventional lipids. In other embodiments, the phenolic lipids are twice boiled CNSL, and conventional lipid raw materials include but are not limited to animal fats, animal oils, microbial oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, greases or any two or more of them in combination. Vegetable oils and / or vegetable oils include but are not limited to corn oil, inedible corn oil, Brazilian palm oil, carina oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acids, palm oil, palm oil fatty acid distillate, jatropha oil, palm kernel oil, sunflower oil, castor oil, camellia oil, algae oil, oil from halophilic objects, and any two or more of them in combination. They can be classified as rough, degummed and RBD (refined, bleached and deodorized) grades, depending on the level of pretreatment and residual phosphorus and metal content. However, any of these grades can be used in the present invention. Animal fat and / or oil used above include but are not limited to inedible tallow, edible tallow, technical grade tallow, float tallow, lard, poultry fat, poultry oil, fish fat, fish oil, and any two or more of them in combination. Grease may include but are not limited to butter, palm oil, waste vegetable oil, restaurant grease, from municipal such as water treatment facilities collection grease, from the used oil of industrial packaged food operation, and any two or more of them in combination mixture. Depending on the pretreatment level, such bio-renewable lipid raw material can contain about 1wppm to about 100wppm phosphorus and about 1wppm to about 100wppm total metal (mainly sodium, potassium, magnesium, calcium, iron and copper). Conventional lipids can also contain up to 20% by weight of free fatty acids. Conventional lipids can include about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 30 wt %, about 32 wt %, about 34 wt %, about 36 wt %, about 38 wt %, about 40 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, or any range including and / or between any two of these values.

[0063] The blended stock with phenolic lipids provides better oxidative stability than conventional stocks, as measured by the AOCS Cd 12b-92 Rancimat method. In certain embodiments, the blended stock of the present invention has an induction time of greater than 10 hours at a test temperature of 110°C according to AOCS Cd 12b-92. In an embodiment, the blended stock has an induction time of greater than 12 hours at a test temperature of 110°C according to AOCS Cd 12b-92.

[0064] The blended feedstock comprising phenolic lipids may be stored in carbon steel tanks for further processing and hydrodeoxygenation as described above for the first embodiment.

[0065] Fourth embodiment of the present invention

[0066] The decarboxylated phenolic lipids are introduced into a petroleum hydroprocessing unit at an inclusion rate of about 1 to about 20 weight %. In other embodiments, the hydroprocessing unit is a diesel hydroprocessor in which the straight-run diesel from a crude distillation unit is desulfurized. In a preferred embodiment, the decarboxylated phenolic lipids are double-boiled CNSL having less than 3wppm phosphorus, less than 2wppm phosphorus, or less than 1wppm phosphorus. In these embodiments, the corresponding total metals in the double-boiled CNSL are less than 3wppm, less than 2wppm, or less than 1wppm. The diesel hydroprocessor includes one or more CoMo and / or NiMo catalyst beds and is operated at a WABT value of 630 to 750°F and a pressure of 100 to 2400psig (typically 200-1000psig). The sulfur content of the straight-run diesel is at most 0.6 weight %, typically 0.1-0.5 weight %. In an embodiment, the straight run diesel feed is partially or completely replaced with light gas oil, or replaced with a cracking feedstock such as light vacuum gas oil or light cycle oil (whose sulfur content is as high as 1.3 weight %, or 0.6 to 1.3 weight %). The diesel hydrotreater is operated to provide a hydrotreated diesel having 15wppm or less sulfur, preferably 10wppm or less sulfur. In an embodiment, the sulfur content of the hydrotreated diesel is 5-10wppm and the biomass carbon content is 1-20 weight %, measured by conventional test method ASTM D6866. Hydrodeoxygenation of the biomass component is achieved while avoiding the formation of CO and CO 2 by-product, thereby avoiding the inhibition of HDS and HDN activity and the formation of aqueous carbonic acid by-product.

[0067] Example

[0068] Example 1

[0069] Two identical pilot plant reactors were charged with two catalyst beds in the same manner. The top bed included 8cc of low activity Mo catalyst, and the bottom bed was charged with 20cc of high activity NiMo catalyst. Each catalyst bed was diluted with inert glass beads of 70-100 mesh size in a 1:1 volume ratio.

[0070] Both catalysts were in the oxide form at loading and were reduced to the active sulfide form during startup. The sulfidation procedure had a low temperature maintained at about 400°F and a high temperature maintained at 650°F (at H 2 S breakout).

[0071] Commercially available canola oil was used to confirm the catalyst activity in each reactor before switching to phenolic lipid feedstock. Both reactors were operated under the following conditions: 1 h -1 LHSV, 3:1 solvent:oil ratio (using SOLTROL 220 as solvent), 1800 psi hydrogen pressure and similar stoichiometric excess hydrogen (where the actual hydrogen to phenolic lipid ratio was about 8600 SCF / Bbl).

[0072] Two different phenolic lipid feedstocks were used: (1) crude cashew nut shell liquid (CNSL), and (2) double boiled CNSL (decarboxylated and distilled CNSL). The crude CNSL was subjected to a pretreatment step prior to blending with canola oil. The pretreatment step included citric acid washing and centrifugation as generally described in the prior art (e.g., U.S. Pat. No. 9,404,604). Both feedstocks were diluted with canola oil to 10 wt% CNSL in the mixed lipids.

[0073] 10 wt% double boiled CNSL in canola oil had less than 1 ppm phosphorus and metals (combined) and only 25 ppm organic nitrogen. In contrast, 10 wt% pretreated crude CNSL in canola oil had significantly higher concentrations of these contaminants, with 30 ppm potassium, 5 ppm sodium, and 167 ppm organic nitrogen.

[0074] The reactor was operated isothermally at different temperature conditions summarized in Table 1. The hydrocarbon phase from the steady-state HDO product was analyzed for residual oxygen, cloud point, aromatic content, and bromine index. Oxygen analysis was performed using fast neutron activation analysis (FNAA) with a detection limit of 0.02 wt%.

[0075] Table 1. Selected physical and chemical properties of the HDO products of Example 1 (a)

[0076]

[0077] Note:

[0078] (a) Test methods are shown in parentheses; all results are from the same reactor unless otherwise stated.

[0079] (b) The entire reactor feed was diluted with 3:1 solvent.

[0080] (c) Results from the second reactor system.

[0081] It is observed from Table 1 that HDO of feedstocks containing both crude and twice boiled (decarboxylated) CNSL according to the present invention produced hydrocarbons with no detectable oxygen at all reactor temperatures tested. According to the Bromine Index, the saturation of hydrocarbons based on phenolic lipids increases with temperature, and the hydrocarbon cloud point increases significantly. No similar relationship has been reported in HDO hydrocarbons from conventional non-phenolic fatty acid lipids. Therefore, the optimal HDO conditions for producing hydrocarbon fuels (whose cloud points are lower than hydrocarbons from non-phenolic fatty acid lipids) from phenolic lipids appear to be a WABT of 600-620°F.

[0082] Example 2

[0083] A sample product of the hydrodeoxygenation of the twice boiled CNSL from Example 1 was analyzed by GC with a mass spectrometer detector to determine the reaction products. The analysis was performed with the sample diluted about 10 times in heptane.

[0084] The GC instrument and operating conditions are shown below.

[0085] Agilent 7890GC and 5977B GC

[0086] Column: J&W HP-5ms GC column, 30m, 0.25mm, 0.25μm, Agilent 19091S-433

[0087] Column flow rate: 1mL / min

[0088] Inlet: Separation, 20:1 separation ratio, 250°C

[0089] Oven: 45°C, increase the temperature to 325°C at 15°C / min, and hold for 5 minutes.

[0090] Injection volume: 1 μL

[0091] The chromatogram produced by this experiment is Figure 4 , where product peaks are numbered 1 to 19. Peaks associated with SOLTROL solvent and canola oil HDO conversion (i.e., octadecane, heptadecane, hexadecane, and pentadecane) are not numbered.

[0092] Table 2 provides the identification of each product substance according to the highest probability match with the National Institute of Standards and Technology (NIST) mass spectral database. As observed from Table 2, the main product compound (peak 7) is determined to be n-pentadecylcyclohexane. Pentadecylbenzene (peak 9) is observed as a smaller amount of product. They are all related to the hydrodeoxygenation of cardanol. C20-C22 paraffins (eicosane, heneicosane, docosane) may include the product of canola oil HDO. C24+ hydrocarbons (peaks 16-19) in the reaction products are related to the hydrodeoxygenation of sterols (which may be present in lipids as less unsaponifiable substances).

[0093] Table 2. Figure 4 Identification table of GC peak numbers

[0094]

[0095]

[0096] *Note: The higher the probability, the more reliable the identification. Probability below 20% is very low and cannot be trusted.

[0097] Example 3

[0098] A blend of grease, oils and fats containing used cooking oil (FOG) was tested for oxidative stability with and without CNSL. Distilled CNSL was added to the FOG at concentrations of 1 wt % and 2 wt % in the blended stock. Both samples, as well as a sample of the same FOG without CNSL, were tested for oxidative stability according to AOCS Test Method Cd 12b-92. The test was conducted at 110°C.

[0099] The results are shown in Figure 5 In. Figure 5 It was observed that the oxidative stability increased from an induction time of 6.7 h (without CNSL) to 10.7 h (with 2% CNSL).

[0100] Therefore, the present invention has been described in conjunction with the preferred embodiments of the present invention, and it will be apparent to those skilled in the art that various modifications may be made to the preferred embodiments described herein without departing from the spirit and scope of the present invention. However, it is intended that all such modifications and changes apparent to those skilled in the art will be included within the scope of the following claims.

Claims

1. A lipid having a fused phenolic group attached to the second and third carbons of a carboxylic acid carbon from a fatty acid molecule according to structure II, the lipid having a C3-C18 carbon chain including a carbon-carbon double bond, wherein the phenolic lipid is used as a hydrodeoxygenation feedstock for renewable diesel, and wherein the lipid is optionally decarboxylated prior to the hydrodeoxygenation step, 2. A method for producing a renewable diesel fuel, wherein The following steps are involved: a. combining a phenolic lipid and a hydrocarbon diluent to provide a hydrocarbon-diluted phenolic lipid; b. hydrodeoxygenating the hydrocarbon-diluted phenolic lipids in a reactor to provide a reactor effluent comprising hydrodeoxygenated phenolic lipids; and c. separating the hydrodeoxygenated phenolic lipids from the reactor effluent; d. wherein the hydrodeoxygenated phenolic lipid is a hydrocarbon having an oxygen content of less than 0.1 wt%.

3. The process of claim 2 wherein the reactor comprises a sulfided molybdenum catalyst and is operated at a temperature of 600 to 650°F in the presence of hydrogen at a pressure of 500 to 2700 psig.

4. The method of claim 2, wherein the phenolic lipid is cashew nut shell liquid (CNSL).

5. The method of claim 2, wherein the phenolic lipids are blended with non-phenolic lipids.

6. The method of claim 2, wherein the phenolic lipid is diluted with an alkane.

7. The method according to claim 6, wherein the volume ratio of the phenolic lipid to the alkane is 1:1 to 1:

4.

8. The method of claim 2, wherein the phenolic lipids are partially hydrogenated.

9. The method of claim 2, wherein the sulfided molybdenum catalyst comprises a nickel or cobalt promoter.

10. The method of claim 2, wherein the hydrodeoxygenated phenolic lipid has a bromine index greater than 70.

11. The method of claim 2, wherein the hydrodeoxygenated phenolic lipids are hydrocarbons in the diesel distillation range (150-380°C).

12. The method of claim 11 wherein the hydrocarbons have less than 4 weight percent monoaromatics and no detectable polyaromatics.

13. The method of claim 10, wherein the hydrocarbons comprise C21 hydrocarbons.

14. The method of claim 10, wherein the hydrocarbon comprises an alkylcyclohexane.

15. The method of claim 10, wherein the hydrocarbon is used as a fuel or a fuel component for a compression ignition engine.

16. The process of claim 10, wherein the hydrocarbons are not isomerized.

17. The method of claim 15, wherein the hydrocarbon has a cloud point of 16°C or less.

18. A renewable diesel (RD) fuel comprising: a. n-alkyl cyclohexane compounds; b. less than 0.1 wt% oxygen; c. Bromine index of 70 or higher; d. a monoaromatic content of 1 wt % to 4 wt %; and e. No detectable di-, tri- or polyaromatic hydrocarbons; f. wherein the n-alkyl cyclohexane compound is a product of hydrodeoxygenation of cashew nut shell liquid.

19. A method for storing electricity, wherein The following steps are involved: a. introducing electricity into an electrolyzer to decompose a water stream into a stream of hydrogen and oxygen; b. supplying the hydrogen to a batch reactor containing phenolic lipids; c. hydrodeoxygenating the phenolic lipids in the batch reactor; d. discharging the hydrodeoxygenated phenolic lipids from the batch reactor; and e. wherein the hydrodeoxygenated phenolic lipid is a hydrocarbon having an oxygen content of less than 0.1 wt%.

20. The method of claim 2, wherein the phenolic lipids are decarboxylated prior to hydrodeoxygenation.

21. A blended feed for hydrodeoxygenation comprising phenolic lipids and conventional lipids, wherein: a. The phenolic lipid is twice boiled cashew nut shell liquid; b. the conventional lipids contain at least 5% by weight of free fatty acids; and c. The blended stock has higher oxidative stability than the conventional lipids.

22. The method of claim 21 wherein the blend stock has a Rancimat induction time greater than 10 hours measured at a test temperature of 110°C.

23. A method for producing low sulfur diesel comprising biomass, wherein The following steps are involved: a. providing a combined feed comprising petroleum diesel (straight run, light gas oil, light cycle oil or light vacuum gas oil) having 0.1-1.3 wt % sulfur and phenolic lipids; b. hydrotreating the combined feed in a hydrotreater comprising a CoMo and / or NiMo catalyst; and c. recovering a hydrotreated diesel fuel having less than 15 wppm sulfur; d. wherein the combined feed comprises up to 20 wt% decarboxylated phenolic lipids, and the decarboxylated phenolic lipids are double boiled cashew nut shell liquid.

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