CN104066818B - The hydro-conversion of renewable raw materials - Google Patents

Abstract

Hydrogenating conversion process includes making to comprise the raw material of the recyclable materials catalyst under hydroprocessing conditions with the promotion selected from self-supported catalyst, loaded catalyst and combinations thereof and contacts, and wherein reaction condition may be tailored to make described renewable raw materials be directly translated into the desired product including fatty alcohol, ester, normal paraffin hydrocarbons or a combination thereof.Described catalyst comprises at least one the group vib metal selected from molybdenum and tungsten, a kind of group VIII metal selected from cobalt and nickel so that described raw material changes into any one in fatty alcohol, ester and normal paraffin hydrocarbons.In some embodiments, described method also includes the other step producing various desired product, described desired product includes alhpa olefin (or PAO, by making described fatty alcohol product be dehydrated), lubricant and bright stock (oligomeric from described PAO) and 3 race's lubricants (common oligomeric from described PAO and some short-chain olefins).

Description

Hydroconversion of renewable raw materials

Cross References to Related Applications

This application claims priority to U.S. Patent Application Nos. 13/315,611, 13/315,774, 13/315,575, 13/315,729, 13/315,650, and 13/315,683, all filed December 2011 September 9th. This application claims priority to and has the benefit of the above patent applications, the disclosures of which are incorporated herein by reference.

technical field

The present application generally relates to processes for the conversion of renewable feedstocks to oleochemicals such as fatty alcohols, esters, and n-paraffins by contacting the renewable feedstock with at least one multimetallic catalyst under hydrotreating conditions.

background

Fossil fuels are finite, non-renewable resources formed from decaying plants and animals that are exposed to the heat and pressure of the earth's crust over hundreds of millions of years to convert them into crude oil, coal, natural gas, or heavy oil. However, as the world's petroleum resources are depleted with their ever-increasing prices, many industries worldwide are looking for renewable/sustainable raw materials ("biological resources") to replace petroleum-based materials in their manufacturing processes .

Industrial oleochemicals are used in the manufacture of surfactants, lubricants, fuels, plastics, and more. Oleochemicals include, but are not limited to, fatty alcohols, esters, and paraffins. It would be highly desirable to provide efficient methods of directly converting renewable materials into such products.

One prior art method of converting biological resources such as lipids (e.g., vegetable oils, animal fats, etc.) Alkyl esters or esters of fatty acid methyl esters (FAME). Hydroprocessing is another method of converting biological resources into useful products. However, in U.S. Patent Application No. 2009/0166256, it is disclosed that in the case of biocomponent feedstocks such as vegetable oils and animal fats that typically contain triglycerides and fatty acids, large triglycerides and Fatty acid molecules can competitively adsorb on and block the active sites of the hydroprocessing catalyst. Catalysts with appropriate morphology, structure and optimal catalytic activity that enable the conversion of renewable feedstocks into high-value products in high yields are needed.

Base stocks are commonly used in the manufacture of process oils, white oils, metalworking oils and lubricants used in automotive, industrial applications, and more. It is becoming increasingly difficult to manufacture lubricants from conventional mineral oils which meet certain standards in the automotive industry. There is a need for improved methods of manufacturing lubricants and bright stocks utilizing renewable raw materials as starting sources.

Summary of the invention

In one aspect, a catalytic conversion process is provided comprising contacting a renewable feedstock with at least one self-supported or supported catalyst under hydrotreating conditions to form an effluent and recovering n-paraffin-containing n-paraffins from the effluent. A hydrocarbon fraction, wherein the hydrotreating conditions include a temperature of 446°F to 752°F (230°C to 400°C) and a total reaction pressure of 50 to 3000 psig (0.35 to 20.7 MPa gauge).

In another aspect, a catalytic conversion process is provided comprising contacting a renewable feedstock with at least one self-supported or supported catalyst under hydrotreating conditions to form an effluent and recovering an aliphatic monoester from said effluent A fraction, wherein the hydrotreating conditions include a temperature of 302°F to 554°F (150°C to 290°C) and a total reaction pressure of 50 to 3000 psig (0.35 to 20.7 MPa gauge).

In yet another aspect, there is provided a hydrocarbon conversion process comprising contacting a renewable feedstock with at least one self-supported or supported catalyst under hydrotreating conditions to form an effluent and recovering a fatty alcohol fraction from said effluent, Wherein said hydrotreating conditions include a temperature of 302°F-554°F (150°C-290°C) and a total reaction pressure of 50-3000 psig (0.35-20.7 MPa gauge pressure). In one embodiment, the aliphatic alcohol fraction is further processed to form Guerbet alcohols.

In yet another aspect, a catalytic conversion process is provided wherein a renewable feedstock is contacted with at least one self-supported catalyst or a supported catalyst to form an effluent containing a fatty alcohol, wherein the fatty alcohol is recovered and subsequently treated in a dehydration zone Dehydration is carried out under dehydrating conditions to form alpha-olefin products.

In one embodiment, the alpha-olefin product formed is oligomerized in the oligomerization zone under oligomerization conditions to form oligomers. In yet another embodiment, hydrotreating the formed oligomer at a temperature comprising 302°F to 752°F (150°C to 400°C) and a total reaction pressure of 50 to 3000 psig (0.35 to 20.7 MPa gauge) Hydrogenated under conditions to form base oils.

In the present invention, the promoted self-supported catalyst or the promoted supported catalyst comprises at least one group VIB metal selected from molybdenum and tungsten, at least one group VIII metal selected from cobalt and nickel, the promoter selected from hydroxy-(di)-carboxylic acids having a steric configuration and having the following structure:

Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is saturated, unsaturated, cyclic, acyclic, aromatic, alcohol, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥0.

Brief description of the drawings

Figure 1 is a schematic diagram showing various reaction pathways in the hydroprocessing of renewable feedstocks such as triglycerides to produce various desired products such as long chain n-paraffins, fatty alcohols, fatty acids and esters.

Figure 2 is a schematic showing the formation of various desirable products such as oligomers, esters, Guerbet alcohols and EOR (enhanced oil recovery) surfactants from the upgrading of renewable feedstocks such as triglycerides.

Detailed description of the invention

The following terms are used throughout the specification and shall have the following meanings unless otherwise specified.

"Renewable feedstock" refers to a feedstock other than those obtained from fossil resources such as crude oil, coal, natural gas, sad oil, etc., which is derived in part from plant-based materials such as vegetable fats/oils or including Raw material for biological raw material components of animal fat/oil from algae and fish fat/oil. In one embodiment, the renewable feedstock is a triglyceride-containing renewable feedstock.

"Oleochemicals" means chemicals of biogenic origin, ie obtained from renewable resources of biological origin. This term is recognized as excluding fossil fuels.

"Middle distillates" are hydrocarbon products having a boiling range from 250°F to 1100°F (121°C to 593°C). The term "middle distillate" includes jet fuel, kerosene, diesel, heating oil boiling range fractions. It may also include a portion of naphtha or light oil. "Jet fuel" is a hydrocarbon product having a boiling range within the jet fuel boiling range. The term "jet fuel boiling range" refers to hydrocarbons having a boiling range from 280°F to 572°F (138°C to 300°C). The term "diesel fuel boiling range" refers to hydrocarbons having a boiling range from 250°F to 1000°F (121°C to 538°C). "Boiling range" is 10 vol% boiling point - final boiling point (99.5 vol %), inclusive, as measured by ASTM D2887-08 ("Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography Range Distribution of Petroleum Fractions by Gas Chromatography)") measurement.

"Triglycerides" refers to the class of molecules having the general formula (1):

wherein R, R and R are independently aliphatic residues having ^6-22 carbon atoms ⁽ eg, 8-20 carbon atoms or 10-16 carbon atoms). The term "aliphatic" refers to a straight (ie, unbranched) or branched, substituted or unsubstituted hydrocarbon chain that is fully saturated or contains one or more units of unsaturation.

"Fatty alcohol" means a primary aliphatic alcohol having typically 8-24 carbon atoms, typically 8-18 carbon atoms, per molecule.

"Aliphatic monoester" refers to a compound having the general formula (2):

wherein ^R3 and ^R4 are independently alkyl moieties. In some embodiments, the aliphatic ester has 16-40 carbon atoms (eg, 18-36 or 20-34 carbon atoms) per molecule. The esters are useful as lubricants.

"Alkane" refers to any saturated hydrocarbon compound, such as an alkane having the formula C _n H( _2n + ₂ ), where n is a non-zero positive integer.

"N-paraffin" means a saturated straight chain hydrocarbon.

"Isoparaffin" means a saturated branched chain hydrocarbon.

"Hydroconversion" is used interchangeably with the term "hydroprocessing" and refers to any process performed in the presence of hydrogen and a catalyst. Such processes include, but are not limited to, methanation, water gas shift reaction, hydrogenation, hydrotreating, hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrodearomatization, hydroisomerization, Hydrodewaxing and hydrocracking including selective hydrocracking.

"Isomerization" refers to a catalytic process in which paraffins are at least partially converted to their isomers containing more branches or vice versa, for example normal paraffins to isoparaffins. The isomerization typically proceeds via catalytic pathways.

"Supported catalyst" refers to a catalyst in which the active component, eg, a Group VIII and VIB metal or a compound thereof, is deposited on a support.

"Self-supported catalyst" is used interchangeably with "unsupported catalyst" or "bulk catalyst" and refers to a catalyst composition that does not have a conventional catalyst form with a prefabricated shaped catalyst support that is subsequently Or deposited to load the metal compound on the carrier. In one embodiment, the self-supported catalyst is formed via precipitation. In another embodiment, the self-supporting catalyst has a binder incorporated into the catalyst composition. In yet another embodiment, the self-supported catalyst is formed from a metal compound without any binder.

In one embodiment, "catalyst precursor" refers to a compound comprising a metal selected from Group IIA, IIB, IVA, Group VIII, and combinations thereof (e.g., one or more Group IIA metals, one or more at least one metal of a Group IIB metal, one or more Group IVA metals, one or more Group VIII metals, and combinations thereof); at least one Group VIB metal; and optionally one or more organic oxygen-containing accelerators , and the compound can be used directly (as a catalyst) after renewable feedstock upgrading or can be sulfided for use as a sulfided hydroprocessing catalyst.

"Group IIA" or "Group IIA metal" means beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), Radium (Ra) and combinations thereof.

"Group IIB" or "Group IIB metal" refers to zinc (Zn), cadmium (Cd), mercury (Hg), and combinations thereof in any of elemental, compound, or ionic form.

"Group IVA" or "Group IVA metal" refers to germanium (Ge), tin (Sn), or lead (Pb), and combinations thereof, in any of elemental, compound, or ionic form.

"Group VIB" or "Group VIB metal" refers to chromium (Cr), molybdenum (Mo), tungsten (W), and combinations thereof in any of elemental, compound, or ionic form.

"Group VIII" or "Group VIII metal" means iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Ro), in any of elemental, compound, or ionic form Palladium (Pd), Osmium (Os), Iridium (Ir), Platinum (Pt), and combinations thereof.

The Periodic Table of the Elements refers to the edition published by CRC Press, 88th Edition (2007-2008) in the CRC Handbook of Chemistry and Medicine. The names of element families in the periodic table are given here in Chemical Abstracts Service (CAS) notation.

"Conversion" refers to the amount of triglycerides in the feed that is converted to compounds other than triglycerides. Conversions are expressed as weight percent based on triglycerides in the feed. "Selectivity" is expressed as weight percent based on converted triglycerides.

"Noble metal" means a metal selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.

"Promoter" refers to an organic reagent that strongly interacts (chemically or physically) with an inorganic reagent in a reaction to form a catalyst or catalyst precursor, causing changes in structure, surface morphology and composition, which in turn result in enhanced catalytic activity.

"Presulfurization" or "presulfided" refers to the sulfidation of the catalyst precursor under sulfidation conditions in the presence of a sulfidation agent such as H2S or dimethylsulfide (DMDS ₎ prior to contact with the feedstock in the upgrading process.

Feedstock: The feedstock consists essentially of renewable feedstock (greater than 99% by weight), which in one embodiment has less than 1% by weight petroleum feedstock, and in a second embodiment has less than 2% by weight petroleum feedstock feedstock, and in a third embodiment, it has less than 5% by weight petroleum feedstock. In another embodiment, the feedstock is a mixture of renewable sources and petroleum feedstock, wherein the petroleum feedstock is up to 50% by weight. In one embodiment, the amount of petroleum feedstock is 1-99% by weight, with the remainder being renewable feedstock; in a second embodiment, the amount of petroleum feedstock is 10-90% by weight, and in a third embodiment, The amount of petroleum raw material is 20-80% by weight. In another embodiment, the feedstock is a pure renewable feedstock (consisting only of renewable feedstock), containing no petroleum feedstocks.

The renewable feedstocks that may be used include any of those feedstocks comprising triglycerides. The feedstock is typically derived from a biomass source selected from crops, plants, microalgae, animal fats, and combinations thereof. The feedstock typically comprises at least 25% by weight triglycerides (eg, at least 50%, 75%, 90%, or 95% by weight triglycerides). In general, any biological source of lipids can serve as the biomass from which the feedstock can be obtained. Exemplary raw materials include, but are not limited to, canola oil, coconut oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, and the like.

Reaction pathways: In the conversion of renewable feedstocks such as triglycerides, in one embodiment the reaction pathways are as shown in Figure 1 where various products are formed such as long chain n-paraffins (jet and diesel range materials ), long-chain primary alcohols and fatty acids. Depending on the reaction conditions, esters may also be formed as reaction products of long-chain primary alcohols and fatty acid products.

In one embodiment, the present invention involves tailoring the reaction conditions to optimize (i.e., maximize) the formation of specific products, such as alkanes, alcohols and/or esters, using a group selected from the group consisting of hydroxyl groups having the structure -Promoter-promoted hydrotreating catalysts for (two)-carboxylic acids:

Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is saturated, unsaturated, cyclic, acyclic, aromatic, alcohol, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥0. "Hydroxy-(di)-carboxylic acid" means a hydroxycarboxylic acid or a hydroxydicarboxylic acid. Examples include, but are not limited to, (R,S)-malic acidHOOC- _CH2 -CHOH-COOH or maleic acid HOOC-CH=CH-COOH. In one embodiment, the promoter is present in an amount of at least 0.05 molar multiples of the total moles of the Group VIB metal and at least one other metal, such as a Group VIII metal. In one embodiment, the promoter is present in an amount ranging from 0.05 to about 1000 molar multiples of the total moles of metal.

Regarding the formation of paraffins (jet/diesel range hydrocarbons) from triglycerides, there are three basic reaction pathways:

Hydrodecarboxylation:

(RCOO) ₃ C ₃ H ₅ +3H ₂ →3RH+C ₃ H ₈ +3CO ₂ (A)

Hydrodecarbonylation:

(RCOO) ₃ C ₃ H ₅ +6H ₂ →3RH+C ₃ H ₈ +3CO+3H ₂ O (B)

Hydrodeoxygenation:

(RCOO) ₃ C ₃ H ₅ +12H ₂ →3RCH ₃ +C ₃ H ₈ +6H ₂ O. (C)

As shown, the hydrogen consumption varies according to the different reaction pathways. Hydrogen consumption increases as hydrotreating progresses harshly, ie from hydrodecarboxylation via hydrodecarbonylation to hydrodeoxygenation. The invention also relates to tailoring reaction conditions to optimize the economy of hydrogen consumption.

Promoted Catalyst - Self-Supported Catalyst: In one embodiment, the catalyst for renewable feedstock upgrading is a promoted self-supported catalyst derived from a catalyst precursor. The catalyst precursor may be a hydroxide or oxide material prepared from at least one Group VIB metal precursor feed and at least one other metal precursor feed. The at least one other metal precursor, which is used interchangeably with ^MP , refers to a material that enhances the activity of the catalyst (compared to a catalyst without the at least one other metal, such as a catalyst with only a Group VIB metal), wherein the promoter is present in an amount of at least 0.05 to about 5 molar multiples of the total moles of the Group VIB metal and at least one other metal, such as a Group VIII metal. In one embodiment, the promoter is present in up to 1000 molar multiples of the total moles of the metal.

The resulting self-supported or unsupported catalyst precursor can be converted into a hydroconversion catalyst (become catalytically active) upon sulfidation. However, the self-supported catalyst precursor itself is used in the conversion of renewable feedstocks (as a catalyst), or it may be sulfided prior to use or in situ in the reactor in the presence of a sulfiding agent. In one embodiment, the self-supported catalyst precursor is used unsulfided, with or without any addition of a sulfiding agent (e.g., H2S ₎ to the reactor system, or is the feed Inherent, even for the hydroconversion of feedstocks consisting essentially of renewable materials (in the absence of any sulfur as sulfiding agent in the feed).

In one embodiment, self-supporting multimetal oxides can also be used. The self-supporting multi-metal oxide comprises at least one group VIII metal and at least two group VIB metals. In one embodiment, the ratio of Group VIB metal to Group VIII metal in the precursor is from about 10:1 to about 1:10. In another embodiment, the oxide catalyst precursor is represented by the formula: (X) _b (Mo) _c (W) _d O _f , wherein X is Ni or Co, Mo is molybdenum, W is tungsten, b: The molar ratio of (c+d) is 0.5:1-3:1 (for example, 0.75:1-1.5:1, or 0.75:1-1.25:1), and the molar ratio of c:d is >0.01:1 (for example, greater than 0.1:1, 1:10-10:1, or 1:3-3:1), and f=[2b+6(c+d)]/2. The oxide catalyst precursor also comprises one or more promoters L. In one embodiment, the self-supported catalyst precursor has the formula (NiL) _x (Mo _y W _1-y )O _(x+3) , wherein L refers to one or more promoters; and wherein x: (1-y) is 1.7-2.4; and y is 0.25-0.67. The oxide precursor is produced by combining a Group VIB metal and a Group VIII metal, forming a product, and subsequently calcining the resulting product.

In another embodiment, the catalyst precursor is in the form of a hydroxide compound comprising at least one Group VIII metal and at least two Group VIB metals. In one embodiment, the hydroxide catalyst precursor is represented by the formula: A _v [(M ^P )(OH) _x (L) ^ny ] _z ( ^{M VIB} _{O 4} ), wherein A is one or more Monovalent cationic species; MP has +2 or +4 oxidation state ( ^P ) depending on the metal used; L is one or more oxygen-containing promoters, and L has a neutral or negative charge n≤0; M ^VIB is at least one group VIB metal having an oxidation state of +6; M ^P :M ^VIB has an atomic ratio between 100:1 and 1:100; v-2+P*zx*z+n*y*z =0; and 0<v≤2;0<x≤P;0<y≤-P/n;0<z. In one embodiment, the catalyst precursor is electrically neutral with no net positive or negative charge.

In one embodiment, A is selected from alkali metal cations, ammonium cations, organoammonium cations and phosphonium cations.

In one embodiment, ^MP has an oxidation state of +2 or +4. ^MP is at least one of a Group IIA metal, a Group IIB metal, a Group IVA metal, a Group VIII metal, and combinations thereof. In one embodiment, MP is at least one Group VIII metal, wherein ^{MP has an oxidation state P of} +2. In another embodiment, MP is selected from Group ^IIB metals, Group IVA metals, and combinations thereof. In one embodiment, ^MP is selected from Group IIB metals and Group VIA metals in their elemental, compound or ionic form, such as zinc, cadmium, mercury, germanium, tin or lead, and combinations thereof. In another embodiment, ^MP is a Group IIA metal compound selected from the group consisting of magnesium, calcium, strontium and barium compounds. ^MP can be in solution or partially in the solid state, such as water-soluble compounds such as carbonates, hydroxides, fumarates, phosphates, phosphites, sulfides, molybdates, tungstates, oxidized their mixtures.

In one embodiment, the accelerator L has a neutral or negative charge n≦0. Examples of accelerator L include, but are not limited to, carboxylates, carboxylic acids, aldehydes, ketones, enolate forms of aldehydes, enolate forms of ketones, and hemiacetals; organic acid addition salts such as formic acid, acetic acid, propane Acid, maleic acid, malic acid, cluconic acid, fumaric acid, succinic acid, tartaric acid, citric acid, oxalic acid, glyoxylic acid, aspartic acid, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, aromatic Sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid and aryl carboxylic acids; compounds containing carboxylates such as maleic anhydride, formates, acetates, propionates, butyrates, valerates, Hexanoates, dicarboxylates, and combinations thereof.

In one embodiment, M ^VIB is at least one Group VIB metal having an oxidation state of +6. In another embodiment, M ^VIB is a mixture of at least two Group VIB metals such as molybdenum and tungsten. M ^VIB can be in solution or partially in the solid state. In one embodiment, ^{MP:M VIB has} a molar ratio of 10:1 to 1:10.

In one embodiment, the self-supported catalyst is prepared from a mixed metal sulfide ("MMS") catalyst precursor characterized by having an optimized Ni:Mo:W composition with a Ni/W molar ratio of 1.62 ≤Ni/W≤2.5, the molar ratio of W/Mo is in the range of 0.5≤W/Mo≤6.0, and the molar ratio of Ni/(Mo+W) is in the range of 0.57<Ni/(Mo+W)<2.1. In another embodiment, the MMS catalyst precursor comprises nickel, molybdenum, and tungsten in relative proportions within a composition range defined by four points ABCD in a ternary phase diagram, where the mole fractions of the four points ABCD are Defined by: A (Ni _x =0.36, Mo _x =0.41, W _x =0.22); B (Ni _y =0.45, Mo _y =0.36, W _y =0.18); C (Ni _z =0.58, Mo _z = 0.06, W _z =0.36) and D (Ni _w =0.68, Mo _w =0.05, W _w =0.27). The MMS catalyst precursor can be used directly for the upgrading of renewable feedstocks with or without presulfidation or with or without any sulfiding agents present or added to the feedstock.

Further details regarding the description of catalyst precursors and the self-supported catalysts they form are described in a number of patents and patent applications, including U.S. Patent Nos. 6,620,313号、6,635,599号、6,652,738号、6,758,963号、6,783,663号、6,860,987号、7,179,366号、7,229,548号、7,232,515号、7,288,182号、7,544,285号、7,615,196号、7,803,735号、7,807,599号、7,816,298号、7,838,696号、7,910,761号, No. 7,931,799, No. 7,964,524, No. 7,964,525, No. 7,964,526, No. 8,058,203 and US Patent Application Publications No. 2007/0090024, 2009/0107886, 2009/0107883, 2009/0107889 and 2009/3011. way is included in this article.

Embodiments of methods of making self-supported catalyst precursors are as described in the references identified above and incorporated herein by reference. In one embodiment, the first step is a mixing step, wherein at least one Group VIB metal precursor feed and at least one other metal precursor feed are combined in a precipitation step (also referred to as cogelation or co-precipitation), in which the catalyst precursors form as a gel. This precipitation (or "co-gelation") occurs at a temperature and a pH at which the Group VIB metal compound and at least one other metal compound precipitate (eg, form a gel). In one embodiment, the temperature is from 25°C to 350°C and the pressure is from 0-3000 psig (0-20.7 MPa gauge). The pH of the reaction mixture can increase or decrease the rate of precipitation (cogelation) depending on the desired properties of the catalyst precursor product, eg, acidic catalyst precursor. In one embodiment, the mixture is maintained at its natural pH during the reacting step. In one embodiment, the pH is maintained in the range of _3-9 ; and in a second embodiment, the pH is maintained in the range of 5-8.

Promoted Catalyst - Self-Supported Catalyst: In another embodiment, the hydroprocessing catalyst is selected from supported catalysts suitable for the hydroconversion of renewable feedstocks. The catalyst comprises at least one metal component selected from group VIII metals and/or at least one metal component selected from group VIB metals. Group VIII metals include iron (Fe), cobalt (Co) and nickel (Ni). Noble metals such as palladium (Pd) and/or platinum (Pt) may be included in the hydroprocessing catalyst. Group VIB metals include chromium (Cr), molybdenum (Mo) and tungsten (W). The Group VIII metal can be present in the catalyst in an amount of 0.5-25% by weight (e.g., 2-20% by weight, 3-10% by weight, 5-10% by weight, or 5-8% by weight) and the Group VIB metal can be 0.5-25% by weight (such as 5-20% by weight, or 10-15% by weight) is present in the catalyst in an amount calculated per 100 parts by weight of the metal compound in the total catalyst, wherein the weight percentage is based on the The weight of the previous catalyst. In one embodiment, the total weight percent of metals used in the hydroprocessing catalyst is at least 5 wt%. The remainder of the catalyst may consist of supported materials, although other components (eg, fillers, molecular sieves, etc., or combinations thereof) may optionally be present.

The metal components in the supported catalyst may be in oxide and/or sulfide form. If the combination of at least one Group VIII metal component and Group VIB metal component is present as a (mixed) oxide, it may be presulfided prior to its appropriate use in hydrotreating. Suitably, the catalyst generally comprises one or more components of Ni and/or Co and one or more components of Mo and/or W. However, the supported catalyst precursor can be used alone with or without any sulfiding agent (e.g., H2S ₎ addition to the reactor system or with or without a sulfiding agent inherent to the feed. Renewable feedstocks are converted (unsulfurized or as a catalyst), or they can be presulfided prior to use or sulfided in situ in the reactor or in the presence of a sulfiding agent in the feed.

The supported catalyst may be prepared by blending or co-milling the above-mentioned active sources of the metals and the binder. Examples of binders include silica, silicon carbide, amorphous and crystalline silica-alumina, silica-magnesia, aluminum phosphate, boria, titania, zirconia, and the like, and mixtures and cogels thereof. Preferred supports include silica, alumina, alumina-silica and crystalline silica-alumina, especially those materials classified as clay or zeolitic materials. Particularly preferred support materials include alumina, silica and alumina-silica, especially alumina or silica. Other components such as phosphorus can be added as needed to tailor the catalyst particles to the desired application. The blended components can thus be shaped such as by extrusion, drying, and calcining at temperatures up to 1200°F (649°C) to make the finished catalyst. Alternatively, other methods of preparing the amorphous catalyst include preparing oxide binder particles such as by extrusion, drying and calcination, followed by depositing the aforementioned metals on the oxide particles using methods such as impregnation. Supported catalysts containing the aforementioned metals can thus be further dried and calcined prior to use as hydrotreating catalysts.

In one embodiment, the supported catalyst is a hydroprocessing catalyst prepared as disclosed in US20090298677A1, the relevant disclosure of which is incorporated herein by reference, by depositing at least one group VIB group comprising the periodic table of elements A composition of metal and at least one Group VIII metal, optionally a phosphorous-containing acidic component, and at least one promoter onto a support with water pore volume, deposited onto the support with water pore volume, and subsequently in The impregnated carrier is prepared by calcining the impregnated carrier at a temperature greater than 200° C. and lower than the decomposition temperature of the accelerator. In one embodiment, the Group VIB metal is selected from molybdenum Mo and tungsten W. The Group VIII metal is selected from cobalt Co and nickel Ni. The accelerator is present in an amount ranging from 0.05 to about 5 molar multiples of the total moles of the Group VIB and Group VIII metals. In one embodiment, the molar ratio of the Group VIII metal to the Group VIB metal is from about 0.05 to about 0.75.

In one embodiment, the accelerator is selected from the group consisting of hydroxycarboxylic acids, ethylene glycol, glycerol, ethanolamine, polyethylene glycol, hydroquinone, ethylenediamine, ethylenediamine-tetraacetic acid, cysteine, alanine acid, methionine, gluconic acid, pyridine-2,3-dicarboxylic acid, thiophene-2-carboxylic acid, mercaptosuccinic acid, nicotinic acid, lactose and acetone-1,3-dicarboxylic acid. In another embodiment, the accelerator is selected from hydroxycarboxylic acids such as tartaric acid, malic acid, glyceric acid, citric acid and gluconic acid. In yet another embodiment, the accelerator is citric acid.

In one embodiment, the supported catalyst has an average pore size of 1-10 nm (eg, 5-10 nm) and a surface area of 20-400 m ² /g (eg, 100-300 m ² /g).

Reactor System: The hydroprocessing process used to upgrade the renewable feedstock can be a single or multi-stage reactor system. In one embodiment, the method utilizes a single stage system. The reactor system can be any reactor type. In one embodiment, the feedstock is processed in a fixed bed reactor. In one embodiment, unreacted triglycerides can be recycled to the reactors of the single-stage reactor system (having only one reactor) or in the multi-stage reactor system (having multiple reactors). in one of the reactors for further processing to maximize the yield of the desired product.

In one embodiment, the reactor system comprises at least two reactors in series of different reactors employing the same or different catalysts. In another embodiment, the reactor comprises a single reactor having at least two catalyst zones, wherein the different catalyst zones utilize the same or different catalysts. In a third embodiment, the system is a single reactor containing a single catalyst type, self-supported catalyst or supported catalyst.

In one embodiment of the reactor system employing different catalysts, the different catalysts are employed in a layered or stacked bed reactor system. "Layered" or "stacked bed" means a separate catalyst in which a first catalyst is present in a separate catalyst layer, bed, reactor or reaction zone and a second catalyst is downstream of said first catalyst with respect to the flow of feed layer, bed, reactor or reaction zone. In one embodiment of the stacked bed system, said system comprises from about 5 to 95% by volume of said first catalyst, with said second catalyst making up the remainder. In a second embodiment, the volume ratio of the first catalyst is about 30-60% by volume. In a third embodiment, the volume ratio of the first catalyst is from 5 to about 50 volume percent. In one embodiment of the stacked bed system, the first catalyst is a supported catalyst and the second catalyst is a self-supported catalyst.

Hydroprocessing conditions: The hydroprocessing conditions may be selected such that the total conversion of triglycerides in the feedstock is at least 20% by weight (e.g., at least 50%, 60%, 70%, 80% by weight %, 90% by weight or 95% by weight). Suitable hydrotreating conditions may include 302°F to 752°F (150°C to 400°C), such as 383°F to 464°F (195°C to 240°C), 491°F to 662°F (255°C to 350°C), or 491°F -563°F (255°C-295°C) temperature; 50-3000psig (0.35-20.7MPa gauge pressure), such as 800-2000psig (5.5-13.8MPa gauge pressure) or 1600-2000psig (11.0-13.8MPa gauge pressure) Total reaction pressure; a liquid hourly space velocity (LHSV) of 0.1-5 h ⁻¹ , such as 0.5-2 h ⁻¹ ; and a hydrogen feed rate of 0.1-20 MSCF/bbl (thousand standard cubic feet per barrel), such as 1-10 MSCF/bbl . It should be noted that a feed rate of 10 MSCF/bbl is equivalent to 1781 L _H2 /L feed.

In one embodiment, the hydroprocessing conditions include a reaction temperature of at least 446°F (230°C) and a reaction pressure of 50-3000 psig (0.35-20.7 MPa gauge), such that the liquid effluent has at least 90% by weight n-paraffin concentration. In another embodiment, the hydrotreating conditions include a reaction temperature of 302°F-554°F (150°C-290°C) and a total reaction pressure of 50-3000 psig (0.35-20.7 MPa gauge pressure), so that the liquid The effluent has a fatty alcohol concentration of at least 5% by weight. In yet another third embodiment, the hydrotreating conditions comprise a temperature of 302°F to 554°F (150°C to 290°C) and a total reaction pressure of 50 to 3000 psig (0.35 to 20.7 MPa gauge), whereby the The liquid effluent has an aliphatic monoester concentration of at least 5% by weight.

In addition to the fact that reaction conditions can be tailored/optimized such that reaction pathways occur selectively, resulting in desired products, the type of catalyst is chosen as a separate variable or in combination with reaction conditions. Promoted self-supported catalysts can be more active than promoted supported catalysts. In one embodiment of a layered catalyst system having a combination of two different catalyst types, a promoted self-supported catalyst and a promoted supported catalyst, the volume ratio of the promoted self-supported catalyst to the promoted supported catalyst is based on Varies depending on the desired product. For example, in the hydrodecarboxylation/hydrodecarbonylation reaction, a promoted self-supported catalyst is more preferred than a promoted supported catalyst, where compared to reaction pathway (C), the promoted self-supported catalyst Reaction pathways (A) and (B) are more favorable and consume or require less hydrogen.

Hydrodecarboxylation:

(RCOO) ₃ C ₃ H ₅ +3H ₂ →3RH+C ₃ H ₈ +3CO ₂ (A)

Hydrodecarbonylation:

(RCOO) ₃ C ₃ H ₅ +6H ₂ →3RH+C ₃ H ₈ +3CO+3H ₂ O (B)

Hydrodeoxygenation:

(RCOO) ₃ C ₃ H ₅ +12H ₂ → 3RCH ₃ +C ₃ H ₈ +6H ₂ O (C).

In one embodiment using the promoted self-supported catalyst system, a triglyceride conversion of greater than 90% is obtained even for a single reactor system. Additionally, conversions of greater than 90% were obtained even with the use of unsulfided promoted catalyst precursor in a single reactor system and without the addition of any sulfiding agent to the reactor system.

Reactor temperature is another variable that selectively affects the reaction pathway and thus the final product. The higher the reactor temperature (eg, at 500°F or higher), the more favorable are reaction pathways (A) and (B). In the upgrading of feedstocks containing triglycerides, such as soybean oil feed mainly composed of _C18 fatty acids and C16 fatty acids, higher reactor temperatures lead to the formation of _nC18 chains via reaction pathways ( _A ) and (B). nC ₁₇ alkanes (and nC ₁₅ alkanes) rich in alkanes (and nC ₁₆ alkanes), where other variables are held constant, a 50°F increase in reactor temperature (e.g., from 500°F to 550°F) causes nC ₁₇ chain Alkanes increased by at least 10%. Conversely, lower reactor temperatures favor C=O bond cleavage in triglycerides, yielding more _nC18 (and _nC16 ) paraffin products. At reactor temperatures of 550°F or higher and total reaction pressures of 1000 psig or lower, more nC ₁₇ paraffins than nC ₁₈ paraffins are formed.

Another variable that selectively affects the formation of the final product is the overall reaction pressure, for example, again for a soybean oil feed consisting primarily of _C18 fatty acids and C16 fatty acids, lower overall reaction pressure favors reaction pathway ( _A ) and (B), resulting in the formation of more nC ₁₇ paraffins (and nC ₁₅ paraffins) than nC ₁₈ paraffins (and nC ₁₆ paraffins), compared to a total reaction pressure of 1500 psi or higher, other variables held constant, A total reaction pressure of 1000 psi or less causes an increase in nC ₁₇ paraffins of at least 10%.

_In an optimized system such as a soybean oil feed consisting primarily of _C18 fatty acids and C16 fatty acids to form predominantly long chain n-paraffins, the reaction temperature is at least 450°F such that the triglyceride conversion is at least 85% ( That is, less than 15% unconverted triglycerides); in one embodiment, the reaction temperature is at least 500°F (260°C) such that the conversion of triglycerides is at least 90%; in a second embodiment, The triglyceride conversion is at least 95%, and in a third embodiment, the triglyceride conversion is at least 99%.

As indicated, the reaction temperature can be adjusted to suit facility process conditions such as available _H2 feed. In the reaction pathway to form long-chain n-paraffins, the hydrodeoxygenation reaction consumes _four times the amount of _H2 that is required for the hydrodecarboxylation reaction. To accommodate the reduction in _H2 feedstock available to the reaction, while still obtaining the desired jet/diesel end product, in one embodiment, the reaction temperature is maintained at a temperature of at least 550°F, and in a second embodiment , the reaction temperature is maintained at a temperature of at least 600°F. In yet another embodiment and in addition to an increase in reactor temperature, for the combination of superior conversion yield and optimized production of jet/diesel product (e.g., at least 90% effluent product comprising n-paraffins), the total Reaction pressure was maintained at 1200 psi or less.

In one embodiment, to optimize the _H2 consumption and/or utilization of the upgrade system while still achieving the desired jet/diesel end product distribution, the hydrotreating conditions can be adjusted by either: increasing A reactor temperature of at least 50°F, a reaction pressure reduction of at least 500 psi, and combinations thereof such that the available H for the process is reduced by _{10 %} for the system at a time, with a minimum amount of H as triglycerides in the feedstock At least 4 times the molar ratio. Each increase in reactor temperature of at least 50°F or decrease in total reaction pressure of at least 100 psi causes in one embodiment a reduction in hydrogen consumption in the process of at least 10 SCF/barrel of feedstock and in a second embodiment at least a reduction in hydrogen consumption of at least 20 SCF/barrel. Bucket of raw materials.

As shown in Figure 1, multiple reaction pathways can exist for the conversion of renewable feedstocks (e.g., vegetable oils in which the majority of fatty acids are triglycerides) in a reactor system: a) conversion of triglycerides to n-paraffins; b) conversion of triglycerides into complex fatty acids (which accumulate said triglycerides); c) manufacture of fatty alcohols, said fatty acids having the same number of carbon atoms in the molecule as these fatty acids; and d) Transesterification produces esters. All these reactions can occur simultaneously in the reactor system.

In one embodiment, the liquid product of the reaction comprises at least one of the following: paraffins, alcohols, acids, esters (formed from resulting alcohols and acids), unconverted triglycerides (if any) and combinations thereof. The composition depends on the catalyst chosen and the hydrotreating conditions. Under certain reaction conditions, such as at lower temperatures such as 450°F or less (which are less favorable for the formation of n-paraffins), as the temperature decreases, more triglycerides are produced compared to n-paraffins The conversion of esters to alcohols and fatty acids, with fewer n-paraffins, is exemplified with a soybean oil feed consisting mainly of _C18 fatty acids and _C16 fatty acids. Additionally, the lower the temperature, the more esters are formed as the resulting alcohol is transesterified with the fatty acid. Conversely, the higher the temperature, the more alcohol is formed as the temperature increases by 50°F (eg, from 400°F to 450°F), resulting in an increase in the amount of alcohol formed by at least 10%.

As discussed, the hydroprocessing conditions may be selected from any parameter that affects the subsequent level of desired product in the effluent from the reactor. In one aspect, said hydroprocessing parameter is a parameter that achieves the yield of product in said reaction mixture, increases the yield of product, optimizes the selectivity of product in said reactor or its efficient conversion in Triglycerides in the reactor. In one embodiment, the hydroprocessing parameters are selected from reactor temperature, total reaction pressure, and combinations thereof.

Products of the upgrading reaction: The effluent from the hydroprocessing zone will contain a liquid portion and a gaseous portion. The effluent can be passed to one or more separators/fractionators to remove gas phase products (e.g., CO, _CO2 , _H2O , methane, and propane) and to separate one or more complete and/or partially deoxygenated product fractions (eg, n-paraffins, fatty alcohols, and/or aliphatic monoesters). Different feedstocks will result in different carbon distributions of the liquid product. In some embodiments, after product gas removal, at least a portion of the liquid effluent may be combined with a hydrotreated liquid effluent from a different feedstock, such as a petroleum feedstock. Additionally or alternatively, after separation of light end products, a recycled product stream may be recovered for use as an input stream to the upgrading reactor system.

In one embodiment, the effluent consists essentially of n-paraffins. In some embodiments, the effluent comprises at least 75% by weight n-paraffins (eg, at least 80% by weight n-paraffins). In some embodiments, the n-paraffin has 8-24 carbon atoms (eg, 12-18 carbon atoms). It should be noted that the n-paraffins may be used as middle distillate fuels. However, subsequent isomerization of the n-paraffins to iso-paraffins may provide a wider range of products with improved low temperature properties such as freezing and pour points, thereby making the process more versatile and flexible.

In another embodiment, the liquid product comprises fatty alcohols, aliphatic monoesters and n-paraffins. In another embodiment, the product is a fatty alcohol, an aliphatic monoester, or a combination thereof.

In some embodiments, the effluent comprises a fatty alcohol fraction. In one embodiment, the fatty alcohol has 8-24 carbon atoms, and in a second embodiment, the fatty alcohol has 8-18 carbon atoms. In some embodiments, the effluent comprises at least 5% by weight fatty alcohol (eg, at least 10% by weight fatty alcohol). In some embodiments, the effluent has a fatty alcohol selectivity of at least 10% by weight (eg, at least 15%, 20%, or 25% by weight).

In some embodiments, the effluent comprises an aliphatic monoester moiety. In one embodiment, the aliphatic monoester has 18-36 carbon atoms. In some embodiments, the effluent comprises at least 4% by weight aliphatic monoester (eg, at least 7%, 10%, or 13% by weight). In some embodiments, the effluent has an aliphatic monoester selectivity of at least 10% by weight (eg, at least 12%, 15%, or 18% by weight).

Further Product Upgrading: In one embodiment, as shown in Figure 2, the products resulting from hydroprocessing of renewable feedstock after separation/recovery can be further processed to produce various desired products, including PAO (poly-alpha -olefins) or alpha-olefins (by dehydration of fatty alcohol products), lubricants and bright stocks (from oligomerization of PAOs) and Group 3 lubricants (from co-oligomerization of PAOs with some short-chain olefins). The alcohol product can be processed to form drilling fluids, EOR (enhanced oil recovery) surfactants, and the like.

Further Product Upgrading - Catalytic Isomerization: In some embodiments, after recovering the n-paraffins as the final product, the upgrading process further comprises catalytic isomerizing at least some of the n-paraffins to form The step of isomerization products of alkanes. In some embodiments, the catalytic isomerization step results in superior fuel properties (eg, cloud point, pour point, etc.) relative to the unisomerized paraffinic product.

In some embodiments, the isomerizing step is performed using an isomerization catalyst. Suitable such isomerization catalysts may include, but are not limited to, Pt and/or Pd on a support. Suitable supports include, but are not limited to, zeolites CIT-1, IM-5, SSZ-20, SSZ-23, SSZ-24, SSZ-25, SSZ-26, SSZ-31, SSZ-32, SSZ-32, SSZ- 33. SSZ-35, SSZ-36, SSZ-37, SSZ-41, SSZ-42, SSZ-43, SSZ-44, SSZ-46, SSZ-47, SSZ-48, SSZ-51, SSZ-56, SSZ-57, SSZ-58, SSZ-59, SSZ-60, SSZ-61, SSZ-63, SSZ-64, SSZ-65, SSZ-67, SSZ-68, SSZ-69, SSZ-70, SSZ- 71, SSZ-74, SSZ-75, SSZ-76, SSZ-78, SSZ-81, SSZ-82, SSZ-83, SSZ-86, SUZ-4, TNU-9, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, EMT-type zeolite, FAU-type zeolite, FER-type zeolite, MEL-type zeolite, MFI-type zeolite, MTT-type zeolite, MTW-type zeolite , MWW-type zeolites, TON-type zeolites, other molecular sieve materials based on crystalline aluminum phosphate, such as SM-3, SM-7, SAPO-11, SAPO-31, SAPO-41, MAPO-11 and MAPO-31. In some embodiments, the isomerization step comprises a Pt and/or Pd catalyst supported on an acidic support material selected from the group consisting of beta or zeolite Y type molecular sieves, silica, alumina, silica-alumina, and combinations thereof . For other suitable isomerization catalysts, see, eg, US Patent Nos. 4,859,312, 5,158,665, and 5,300,210.

Isomerization conditions may include temperatures from 200°F to 900°F (93°C to 482°C), such as 300°F to 800°F (149°C to 427°C) or 400°F to 800°F (204°C to 427°C); 15- A total reaction pressure of 3000 psig (0.1-20.7 MPa gauge), such as 50-2500 psig (0.3-17.2 MPa gauge); an LHSV of 0.1-10 h ⁻¹ , such as 0.25-5 h ⁻¹ ; and 0.1-30 MSCF/bbl, such as Hydrogen treatment rate of 0.2-20MSCF/bbl or 0.4-10MSCF/bbl.

With regard to the catalytic isomerization step above, in some embodiments, the processes described herein may be carried out by contacting the n-paraffin with a fixed stationary bed, a fixed fluidized bed, or a transport bed of catalyst . In one embodiment, trickle bed operation is employed wherein the feed is trickled through a fixed fixed bed, typically in the presence of hydrogen. For a description of the operation of the catalyst, see US Patent Nos. 6,204,426 and 6,723,889, the relevant disclosures of which are incorporated herein by reference.

In some embodiments, the isomerized product comprises at least 10% by weight isoparaffins (eg, at least 30%, 50%, or 70% by weight isoparaffins). In some embodiments, the isomerized product has a molar ratio of isoparaffins to n-paraffins of at least 5:1 (eg, at least 10:1, 15:1, or 20:1).

In some embodiments, the isomerization product has a temperature of 250°F-1100°F (121°C-593°C), such as 280°F-572°F (138°C-300°C) or 250°F-1000°F (121°C-538°C). °C) boiling range.

In some embodiments, the isomerized product is suitable (or most suitable) for use as a transportation fuel. In some such embodiments, the isomerization product is mixed or blended with existing transportation fuels to create new fuels or improve the properties of existing fuels. Isomerization and blending can be used to adjust and maintain the pour and cloud points of fuels or other products at proper values. In some embodiments, the n-paraffins are blended with other materials prior to catalytic hydrogenation. In some embodiments, the n-paraffins are blended with the isomerization product.

Further product upgrading - dehydration: In one embodiment, after separation of the effluent, fatty alcohols such as 1-hexanol and/or long chain bioalcohols including 1-hexadecanol and the like are produced as end products. The alcohol product is dehydrated under dehydrating conditions to form an alpha-olefin product, for example a bio-1-olefin, such as bio-1-hexene or bio-1-hexadecene. The final bio-olefin product can be further processed to produce bio-lubricant.

Dehydration processes for the conversion of bio-alcohols to alpha-olefin products are disclosed in US20120238788A1 and US20110288352A1, the relevant disclosures of which are incorporated herein by reference. In one embodiment of the dehydration process, the fatty alcohol is heated in the presence of at least the desired catalyst and at a sufficient temperature and optionally with at least one purge gas for a sufficient period of time. In embodiments, the optional purge gas is nitrogen, argon, or a mixture of these two gases. In one embodiment, the reaction conditions include atmospheric pressure, a temperature of 250-420° C., and an LHSV of 1-5 h ⁻¹ . In embodiments, the heating temperature for said dehydration is about 300-420°C or about 360-385°C.

In one embodiment, the catalyst is activated alumina. In another embodiment, the catalyst is an equimolar combination of zinc oxide and aluminum oxide which has been pretreated at a temperature of 800-1000° C. for a period of 24-48 hours, subsequently treated with alkali, washed, air-dried and subsequently Treatment with 0.1-20% by weight of chlorosilane in hydrocarbon solvent.

In some embodiments, fatty alcohols produced from the upgrading of renewable feedstocks may be co-polymerized with other fatty alcohols, such as petroleum-derived fatty alcohols or Fischer-Tropsch derived fatty alcohols, prior to the dehydration step to produce alpha-olefin products. mix.

Further Product Upgrading - Oligomerization: In one embodiment, after the dehydration step, the alpha-olefin product produced can be further processed by oligomerization to form dihydrogen diolefins, optionally with amounts of other desirable higher oligomers. Mixtures of polymers, trimers, tetramers and pentamers. The oligomer products can subsequently be hydrogenated to improve their thermal and oxidative stability. In some embodiments, dehydration, oligomerization, and hydrogenation are each performed in the presence of a dehydration catalyst, oligomerization catalyst, and hydrogenation catalyst, respectively. In some embodiments, dehydration, oligomerization, and hydrogenation can be performed in different reaction zones. In certain embodiments, two or more of dehydration, oligomerization, and hydrogenation can be performed in the same reaction zone. Oligomerization processes to convert such alpha-olefin products are disclosed in US20110288352A1, the relevant disclosures of which are incorporated herein by reference.

In one embodiment of the oligomerization step, the alpha-olefin product produced above is heated over a heterogeneous acidic catalyst such as a sulfonic acid resin, solid phosphoric acid, or an acidic zeolite, or any other suitable catalyst at a moderate temperature (e.g., 100-300 °C) and pressure (eg, 0-1000 psig) to form a blend of the resulting alpha-olefin with a co-oligomer of a light olefin such as butene. Heterogeneous or homogeneous oligomerization catalysts can be used, which are described in G. Busca, "Acid Catalysts in Industrial Hydrocarbon Chemistry" Chem Rev 2007(107) 5366-5410. Other catalysts include acidic solid phase catalysts such as alumina and zeolites (see, eg, US Patent Nos. 3,997,621, 4,663,406, 4,612,406, 4,864,068, and 5,962,604). In certain embodiments, an acidic resin catalyst, such as Amberlyst-35 catalyst, may be employed.

The oligomerization conditions can be optimized as described herein to limit the production of light or heavy components, for example by simplifying downstream fractionation steps during the oligomerization step by appropriate selection of catalyst, reaction time, temperature, pressure, etc. Specific needs of oil products. Additionally, the lighter and/or heavier fractions from the oligomerization reactions may be treated (by eg distillation, etc.) prior to further processing to provide hydrogenated feedstocks such as jet fuel blend feedstocks. Alternatively, the lighter or heavier fractions may be separated after hydrogenation/hydrotreating. Various methods can be used to control the molecular weight distribution of the resulting oligomers, including the formation of primarily dimers, trimers (see, e.g., PCT Patent Application Publication WO 2007 /091862) and tetramers and pentamers (see, eg, US Pat. No. 6,239,321), the relevant disclosures of which are incorporated herein by reference.

Further product upgrading - co-oligomerization: In some cases, the lower branched olefins produced by the dehydration reaction may be smaller than the desired olefins, eg C8 olefins. In one embodiment, smaller oligomeric C4-C8 olefins can be separated from the product mixture and subsequently introduced to an oligomerization reaction zone to co-oligomerize with other long chain alpha-olefins to form a Group 3 lubricant product. In another embodiment, the resulting long chain alpha-olefin olefins can be separated from the product mixture and subsequently introduced to an oligomerization reaction zone to co-oligomerize with some light olefins, such as butenes, to form a Group 3 lubricant product.

Examples: The following illustrative examples are intended to be non-limiting.

Example 1: A soybean feed with an API gravity of 21.6 (0.9223 g/ml) was used as raw material. The triglycerides of soybean oil are mainly derived from five fatty acids (see, eg, D. Firestone, Physical and Chemical Characteristics of Oils, Fats, and Waxes, 2nd Edition, 2006, AOCS Press, 149). Table 1 discloses representative ranges of these fatty acids in soybean oil.

Table 1:

fatty acid carbon atom: double bond weight% Palmitic acid 16:0 9.7-13.3 stearic acid 18:0 3.0-5.4 Oleic acid 18:1 17.7-28.5 Linoleic acid 18:2 49.8-57.1 alpha-linoleic acid 18:3 5.5-9.5

Examples 2-8: Soybean oil feed from Example 1 under hydrotreating conditions in a single reactor over a promoted catalyst based on Ni-Mo-W-maleic acid catalyst precursor (according to U.S. Patent 7,807,599 No. Example 1) and an accelerated catalyst sulfided with dimethyl sulfide gas (according to Example 6 of US Patent No. 7,807,599). Reactor conditions included a hydrogen rate of 8.0 MSCF/bbl and an LHSV of 1.0 h ⁻¹ . Other hydrotreating conditions (reactor temperature and pressure) are listed in Table 2 and Table 3.

The composition of the overall product was determined by gas chromatography (GC) and is listed in Table 2 in % by weight. All liquid paraffin products were n-paraffins with negligible amounts of iso-paraffins formed as determined by GC. Methane and propane are essentially the only other light hydrocarbon products. Water, carbon monoxide (CO) and carbon dioxide (CO ₂ ) are by-products from hydrodeoxygenation, hydrodecarbonylation and/or hydrodecarboxylation.

Table 2:

See examples, hydrotreating at 1900 psig and temperatures of 500°F and 550°F (Examples 4 and ₅ ), _C15 /C16 n-paraffins and _C17 / _C18 n-paraffins products at 500°F The weight ratio was all 0.35 (Example 4). At 550°F (Example 5), the C ₁₅ /C ₁₆ n-paraffin product weight ratio increased to 0.55 and the C ₁₇ /C ₁₈ n-paraffin product weight ratio increased to 0.59. The increased C ₁₅ /C ₁₆ and C ₁₇ /C ₁₈ n-paraffin product ratios indicate that at higher reaction temperatures, the catalyst is less effective for hydrogenation than for hydrodeoxygenation (making C ₁₆ and C ₁₈ n-paraffins and water). Enhanced selectivity of decarboxylation and/or hydrodecarbonylation (production of _C15 and _C17 n-paraffins as well as CO and _CO2 , plus _H2O ). Thus, slightly higher (CO+ _CO2 )/ _H2O product weight ratios are achieved at higher temperatures and reflect a certain selectivity for hydrodecarboxylation and/or hydrodecarbonylation relative to hydrodeoxygenation degree of enhancement.

Referring to the example of hydrotreating at 1000 psig, the _C15 /C16 n-paraffins product weight ratio _at 500°F (Example 6) was 0.56 and the _C17 / _C18 n-paraffins weight ratio was 0.59. At 550°F (Example 7), the C ₁₅ /C ₁₆ n-paraffin product weight ratio increased to 1.02 and the C ₁₇ /C ₁₈ n-paraffin product weight ratio increased to 1.04. Additionally, at 650°F (Example 8), the C ₁₅ /C ₁₆ n-paraffin product weight ratio increased to 1.80 and the C ₁₇ /C ₁₈ n-paraffin product weight ratio increased to 2.03. The increased C ₁₅ /C ₁₆ and C ₁₇ /C ₁₈ n-paraffin product ratios indicate that at higher reaction temperatures, the catalyst is less effective for hydrogenation than for hydrodeoxygenation (making C ₁₆ and C ₁₈ n-paraffins and water). Enhanced selectivity of decarboxylation and/or hydrodecarbonylation (production of _C15 and _C17 n-paraffins as well as CO and _CO2 , plus _H2O ). Thus, slightly higher (CO+CO ₂ )/H ₂ O product weight ratios are achieved at higher temperatures and reflect enhanced selectivity for hydrodecarboxylation and/or hydrodecarbonylation relative to hydrodeoxygenation .

In addition, comparing the results of Examples 4 and 5 (performed at 1900 psig) with those of Examples 6 and 7 (performed at 1000 psig), respectively, relative to hydrodeoxygenation, a lower reaction pressure is achieved for hydrogenation The increased selectivity of decarboxylation and/or hydrodecarbonylation leads to a further reduction in hydrogen consumption.

The conversion of triglycerides and the product selectivity of the hydrotreating operation are listed in Table 3.

table 3:

Examples 9-12: Soybean oil feed from Example 1 under hydroprocessing conditions at various temperatures in a single stage reactor over a promoted hydroprocessing catalyst prepared as disclosed in US20090298677A1 as from Chevron Lummus It was tested on an alumina-supported Ni-Mo catalyst purchased from Global with a median pore diameter of about 8 nm and a specific surface area of about 180 m ² /g. Reactor conditions included a total reaction pressure of 1900 psig (13.1 MPa gauge), a hydrogen rate of 8.0 MSCF/bbl, and an LHSV of 1.0 h ⁻¹ .

The composition of the overall product was determined by gas chromatography (GC) and is listed in Table 4 in % by weight. All liquid paraffin products were n-paraffins with negligible amounts of iso-paraffins formed as determined by GC. Methane and propane are essentially the only other hydrocarbon products. Water, carbon monoxide (CO) and carbon dioxide (CO ₂ ) are by-products from hydrodeoxygenation, hydrodecarbonylation and/or hydrodecarboxylation.

Table 4:

The conversion of triglycerides and the product selectivity of the hydrotreating operation with the supported catalyst are listed in Table 5.

table 5:

Examples 13-14: Soybean oil feed from Example 1 under hydrotreating conditions in a single reactor with a presulfided promoted self-supported catalyst (as used in Examples 2-8) and presulfided The promoted supported catalyst (as used in Examples 9-12) was tested under reaction conditions of 550°F, 1000 psig, 1.0 h ^-1 LHSV, and 8000 scf/bbl fed _H2 rate. All triglycerides in the feed were converted and paraffins were the only components in the liquid product. Table 6 presents the SimDis (simulated distillation by gas chromatography) of the diesel products from these two examples. Promoted self-supported catalysts are more selective than promoted supported catalysts for hydrodecarboxylation-hydrodecarbonylation reactions.

Table 6

Examples 15-16: The soybean oil feed from Example 1 was hydrotreated in a single reactor with a presulfided promoted self-supported catalyst (as used in Examples 2-8) but at 1000 psig Other reaction conditions including a temperature of 600°F, a _H2 rate of 0.5h ⁻¹ LHSV, and a feed of 8000 SCF/bbl were tested at different total reaction pressures of 500 psig and 500 psig. All triglycerides in the feed were converted and paraffins were the only components in the liquid product. Table 7 presents the SimDis (simulated distillation by gas chromatography) of the diesel products from these two examples. Lower pressures are more favorable for the hydrodecarboxylation-hydrodecarbonylation reaction.

Table 7

Examples 17-18: The soybean oil feed from Example 1 was treated in a single reactor with an unsulfurized promoted self-supported catalyst precursor (as used in Examples 2-8, but unsulfurized) and sulfided promoted self-supported catalysts (as used in Examples 2-8), but at a temperature comprising 550°F, a pressure of 1000 psig, 1.0h ^{- 1} LHSV, and 8000 SCF/bbl of H ₂ fed tested under the same reaction conditions. All triglycerides in the feed were converted and paraffins were the only components in the liquid product. Table 8 presents the SimDis (simulated distillation by gas chromatography) of the diesel products from these two examples. Sulfurized promoted self-supported catalysts are more active than unsulfided versions. It should be noted, however, that the reaction proceeds even with unsulfided promoted catalyst precursor.

Table 7

Example 19: The soybean oil feed from Example 1 was used in a single reactor under hydrotreating conditions (500 or 550° F, 1000 psig, 1.0 h ^LHSV and 8000 scf/bbl feed _H2 rate) with Noble Metal Amorphous Catalyst Test under the trade designation ICR-419 from Chevron LumnusGlobal. It should be noted that noble metal catalysts appear to be ineffective for hydrodecarboxylation and hydrodecarbonylation, as shown by the low triglyceride conversions of 57% by weight at 500°F and 88% by weight at 550°F, respectively, and where with Relatively little n-paraffins are formed compared to the amount of fatty alcohols and esters formed.

For the purposes of this specification and the appended claims, unless otherwise indicated, all figures expressing quantities, percentages or ratios, and other numerical values used in the specification and the appended claims, are to be understood in all instances by the term "about "Retouch. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be sought by the present invention. It should be noted that, as used in this specification and the appended claims, the singular forms "a" and "the" include plural references unless expressly and clearly limited to a single reference. As used herein, the term "comprises" and its grammatical variants are intended to be non-limiting, such that the description of listed items does not exclude other similar items that could replace or add to the listed items middle. As used herein, the term "comprising" means including the elements or steps identified after the term, but any stated elements or steps are not exhaustive, and an embodiment may include other elements or steps.

A description of a class of elements, materials, or other components from which individual components or mixtures of components may be selected is intended to include all possible subclass combinations of the listed components and mixtures thereof, unless otherwise stated.

The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be included in the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims. In the range. To the extent inconsistent therewith, all citations are hereby incorporated by reference.

Claims (54)

1. A method for catalytically upgrading feedstock comprising renewable materials consisting essentially of triglycerides, said method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising a catalyst selected from the group consisting of At least one group VIB metal of molybdenum and tungsten, at least one group VIII metal selected from cobalt and nickel, the promoter is selected from substances having a spatial configuration and having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent comprising at least one of n-paraffins, fatty alcohols, aliphatic monoesters, and combinations thereof, Wherein said hydrotreating condition is basically selected according to any one in the following conditions: a reaction temperature of at least 230° C. resulting in a triglyceride conversion of at least 50%; a reaction temperature of at least 230° C. and a total reaction pressure of 0.35-20.7 MPa gauge such that said liquid effluent has a normal paraffin concentration of at least 30% by weight; a reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge, such that the liquid effluent has a fatty alcohol concentration of at least 5% by weight; A reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge allow the liquid effluent to have an aliphatic monoester concentration of at least 5% by weight. 2. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, said method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, a group VIII metal selected from cobalt and nickel, the accelerator selected from substances having a spatial configuration and having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent having a n-paraffin concentration of at least 30% by weight, Wherein the hydrotreating conditions include a temperature of 230° C.-400° C. and a total reaction pressure of 0.35-20.7 MPa gauge pressure. 3. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, said method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, a group VIII metal selected from cobalt and nickel, the accelerator selected from substances having a spatial configuration and having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent having a fatty alcohol concentration of at least 5% by weight, Wherein the hydrotreating conditions include a temperature of 150° C.-290° C. and a total reaction pressure of 0.35-20.7 MPa gauge pressure. 4. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, said method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, a group VIII metal selected from cobalt and nickel, the catalyst being promoted with a promoter selected from substances having a steric configuration and having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent having an aliphatic monoester concentration of at least 5% by weight, Wherein the hydrotreating conditions include a temperature of 150° C.-290° C. and a total reaction pressure of 0.35-20.7 MPa gauge pressure. 5. The method of any one of claims 1-4, wherein the accelerator is present in an amount of at least 0.05 molar multiples of the total moles of the Group VIB and Group VIII metals. 6. The method of claim 5, wherein the promoter is present in an amount of 0.05-1000 mole multiples of the total moles of the Group VIB and Group VIII metals. 7. The method of any one of claims 1-4, wherein the feedstock consists essentially of renewable materials. 8. The method of claim 7, wherein the renewable material is based on vegetable oils and/or animal fats. 9. The method of any one of claims 1-4, wherein the feedstock comprises a mixture of renewable material and petroleum feedstock, wherein the amount of petroleum feedstock is 1-99% by weight and the remainder is renewable material. 10. The method of claim 9, wherein the feedstock comprises a mixture of renewable material and petroleum feedstock, wherein the amount of petroleum feedstock is 20-80% by weight and the remainder is renewable material. 11. The method of any one of claims 1-4, wherein the catalytic upgrading is performed in a single reactor system. 12. The method of any one of claims 1-4, wherein the catalytic upgrading is performed in a reactor system comprising at least two reactors in series employing the same or different promoted catalysts. 13. The method of any one of claims 1-4, wherein the catalytic upgrading is performed in a layered reactor system having a first layer containing a self-supported catalyst and a second layer containing a supported catalyst, Wherein the volume ratio of the self-supported catalyst to the supported catalyst is 5:95-95:5. 14. The method of any one of claims 1-4, wherein the catalyst is contacted with the feedstock without presulfiding. 15. The method of any one of claims 1-4, wherein the catalyst is presulfided prior to contacting the feedstock. 16. The process of any one of claims 1-4, wherein the catalyst is contacted with the feedstock in the absence of any sulfiding agent added or present in the feedstock. 17. The method of any one of claims 1-4, wherein the catalyst is contacted with the feedstock in the presence or addition of a sulfiding agent to the feedstock. 18. The method of any one of claims 1-4, wherein the catalyst is a supported catalyst. 19. The method of any one of claims 1-4, wherein the catalyst is a supported catalyst, and the molar ratio of the Group VIII metal to the Group VIB metal is 0.05-0.75. 20. The method of any one of claims 1-4, wherein the catalyst is a supported catalyst having an average pore size of 1-10 nm and a surface area of 20-400 ^m2 /g. 21. The method of any one of claims 1-4, wherein the promoted catalyst is a self-supported catalyst. 22. The method of claim 21, wherein the self-supported catalyst is a catalyst precursor in direct contact with the feedstock. 23. The method of claim 21, wherein the catalyst is contacted with the feedstock in the absence of any sulfiding agent added or present in the feedstock. 24. The method of claim 21, wherein the catalyst is contacted with the feedstock in the presence or addition of a sulfiding agent to the feedstock. 25. The method of claim 21, wherein the self-supporting catalyst is a catalyst precursor that has been presulfided prior to contacting the feedstock. 26. The method of claim 21, wherein the promoted catalyst is derived from a self- _supported catalyst precursor of the formula A _v [(M ^P )(OH) _x (L) ^ny ] _z (M ^VIB O ₄ ) ,in: A is selected from alkali metal cations, NH ₄ ⁺ , organic ammonium cations and phosphonium cations; MP is at least one of a Group IIA metal, a Group IIB metal, a Group IVA metal, a Group VIII metal, and combinations thereof, ^P being an oxidation state, wherein ^MP has an oxidation state of +2 or +4 depending on the choice of ^MP ; L is an accelerator with neutral or negative charge n≤0; M ^VIB is at least one Group VIB metal having an oxidation state of +6; M ^P :M ^VIB has an atomic ratio between 100:1 and 1:100; v-2+P*z-x*z+n*y*z=0; and 0<v≤2; 0<x≤P; 0<y≤-P/n; 0<z. 27. The method of claim 21, wherein the self-supported catalyst is derived from a self-supported mixed metal sulfide catalyst precursor having a Ni/W molar ratio of 1.62≤Ni/W≤2.5, at 0.5≤W W/Mo molar ratio in the range of /Mo≤6.0 and Ni/(Mo+W) molar ratio in the range of 0.57<Ni/(Mo+W)<2.1. 28. The method of claim 21 , wherein the self-supported catalyst is derived from molar ratios of nickel, molybdenum, and tungsten in relative proportions within the composition range defined by the four points ABCD of the ternary phase diagram. Self-supported mixed metal sulfide catalyst precursor, wherein the mole fractions of the four points ABCD are defined by: A: Ni _x = 0.36, Mo _x = 0.41, W _x = 0.22; B: Ni _y = 0.45, Mo _y = 0.36, W _y = 0.18; C: Ni _z = 0.58, Mo _z = 0.06, W _z = 0.36; and D: Ni _w = 0.68, Mo _w = 0.05, W _w = 0.27. 29. The method of claim 2, wherein the hydrotreating conditions comprise a temperature of at least 288°C such that the recovered liquid effluent has a normal paraffin concentration of at least 90% by weight. 30. The method of claim 2, wherein the hydrotreating conditions comprise a total reaction pressure of 1200 psi or less such that the recovered liquid effluent has a normal paraffin concentration of at least 90% by weight. 31. The method of claim 2, wherein the hydrotreating conditions comprise a temperature of at least 288°C and a total reaction pressure of 1200 psi or less such that the recovered liquid effluent has more _nC17 chains than _nC18 paraffins alkanes. 32. The method of any one of claims 1-2, further comprising catalytic isomerizing at least a portion of the normal paraffins to form isomerized products comprising isoparaffins. 33. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, a group VIII metal selected from cobalt and nickel, and the promoter selected from substances with a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥ 0; the hydroprocessing conditions include a temperature of 230°C-400°C and a total reaction pressure of 0.35-20.7MPa gauge pressure, so that the triglyceride conversion rate is at least 50% by weight; recovering said liquid effluent having a n-paraffin concentration of at least 30% by weight, and Catalytic isomerization of at least a portion of the normal paraffins to form isomerized products comprising isoparaffins. 34. The method of any one of claims 1-2 and 33, wherein the n-paraffin has 8-24 carbon atoms. 35. The method of claim 33, wherein the catalytic isomerization step employs an isomerization catalyst comprising a metal selected from the group consisting of Pt, Pd, and combinations thereof. 36. The method of claim 33, wherein the isomerized product comprises at least 10% by weight isoparaffins. 37. The method of claim 33, wherein the isomerized product has a molar ratio of isoparaffins to n-paraffins of at least 5:1. 38. The method of claim 33, wherein the isomerized product has a boiling range of 121°C to 538°C. 39. The method of any one of claims 1 and 3, further comprising subjecting the fatty alcohol under dehydration conditions in the presence of at least one catalyst for a sufficient time and at a temperature sufficient to form an alpha-olefin product dehydration. 40. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from the group consisting of self-supported catalysts, supported catalysts, and combinations thereof, under hydroprocessing conditions to form a liquid effluent and a gaseous product, the promoted The catalyst comprises at least one Group VIB metal selected from molybdenum and tungsten, one Group VIII metal selected from cobalt and nickel, and the promoter is selected from substances having a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥ 0; the hydrotreating conditions include a temperature of 150°C-290°C and a total reaction pressure of 0.35-20.7MPa gauge pressure, such that the triglyceride conversion rate is at least 10% by weight; recovering said liquid effluent having a fatty alcohol concentration of at least 5% by weight; recovering fatty alcohol product from said liquid effluent; and The fatty alcohol product is dehydrated under dehydration conditions in the presence of at least one catalyst for a sufficient time and at a temperature sufficient to form an alpha-olefin product. 41. The method of claim 40, wherein the alpha-olefin product comprises bio-1-olefins. 42. The method of claim 40, wherein the catalyst is an oxidized catalyst pretreated with base at a temperature of 100-1000°C for 1-48 hours and subsequently treated with 0.1-20% by weight of chlorosilane in a hydrocarbon solvent. An equimolar combination of zinc and alumina. 43. The method of claim 40, further comprising blending other fatty alcohols into the fatty alcohol product prior to the dehydration step to produce an alpha-olefin product. 44. The method of claim 43, wherein the other fatty alcohols comprise at least one of petroleum-derived fatty alcohols, Fischer-Tropsch derived fatty alcohols, and combinations thereof. 45. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, one group VIII metal selected from cobalt and nickel, and the promoter selected from substances having a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥ 0; the hydrotreating conditions include a temperature of 150°C-290°C and a total reaction pressure of 0.35-20.7MPa gauge pressure, such that the triglyceride conversion rate is at least 10% by weight; recovering said liquid effluent having a fatty alcohol concentration of at least 5% by weight; recovering fatty alcohol product from said liquid effluent; dehydrating the fatty alcohol product under dehydration conditions in the presence of at least one catalyst for a sufficient time and at a temperature sufficient to form an alpha-olefin product; and The alpha-olefin product is reacted over a heterogeneous acidic catalyst at a temperature of 100-300°C and a pressure of 0-1000 psig to form a blend of oligomers. 46. The method of claim 45, wherein the heterogeneous acidic catalyst is selected from the group consisting of sulfonic acid resins, solid phosphoric acid, acidic zeolites, ionic liquids, and combinations thereof. 47. A method of optimizing hydrogen consumption in catalytic upgrading of a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, one group VIII metal selected from cobalt and nickel, and the promoter selected from substances having a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥ 0; the hydrotreating conditions include a reactor temperature of 230°C-400°C and a total reaction pressure of 0.35-20.7MPa gauge; and recovering said liquid effluent having a n-paraffin concentration of at least 30% by weight, wherein the hydroprocessing conditions are adjusted according to any of the following conditions: increasing the reactor temperature by at least 50°F, reducing the total reaction pressure by at least 100 psi, and combinations thereof such that hydrogen consumption in the process is reduced by at least 10SCF/barrel raw material. 48. The process of claim 47, wherein each increase in reactor temperature of at least 50°F or each decrease in said total reaction pressure of at least 100 psi results in a decrease in hydrogen consumption in said process of at least 20 SCF/barrel of feedstock. 49. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, a group VIII metal selected from cobalt and nickel, and the promoter selected from substances with a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent comprising at least one of n-paraffins, fatty alcohols, aliphatic monoesters, and combinations thereof, recovering n-paraffin products from said liquid effluent; catalytically isomerizing at least a portion of the n-paraffin product to form an isomerized product comprising isoparaffins; Wherein said hydrotreating condition is basically selected according to any one in the following conditions: a reaction temperature of at least 230° C. such that the triglyceride conversion is at least 50% by weight; a reaction temperature of at least 230° C. and a total reaction pressure of 0.35-20.7 MPa gauge such that the liquid effluent has a normal paraffin concentration of at least 30% by weight; a reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge, such that the liquid effluent has a fatty alcohol concentration of at least 5% by weight; A reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge allow the liquid effluent to have an aliphatic monoester concentration of at least 5% by weight. 50. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from self-supported catalysts, supported catalysts, and combinations thereof, the catalyst comprising At least one group VIB metal selected from molybdenum and tungsten, a group VIII metal selected from cobalt and nickel, and the promoter selected from substances with a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent comprising at least one of n-paraffins, fatty alcohols, aliphatic monoesters, and combinations thereof, recovering fatty alcohol product from said liquid effluent; dehydrating the fatty alcohol under dehydrating conditions in the presence of at least one catalyst for a sufficient time and at a temperature sufficient to form an alpha-olefin product; Wherein said hydrotreating condition is basically selected according to any one in the following conditions: a reaction temperature of at least 230° C. such that the triglyceride conversion is at least 50% by weight; A reaction temperature of at least 230° C. and a total reaction pressure of 0.35-20.7 MPa gauge such that said liquid effluent has a normal paraffin concentration of at least 30% by weight; a reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge, such that the liquid effluent has a fatty alcohol concentration of at least 5% by weight; A reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge allow the liquid effluent to have an aliphatic monoester concentration of at least 5% by weight. 51. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from the group consisting of promoted self-supported catalysts, promoted supported catalysts, and combinations thereof under hydroprocessing conditions to form a liquid effluent and a gaseous product, the The catalyst comprises at least one Group VIB metal selected from molybdenum and tungsten, a Group VIII metal selected from cobalt and nickel, and the promoter is selected from substances having a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , where m and n are integers ≥ 0; and recovering said liquid effluent comprising at least one of n-paraffins, fatty alcohols, aliphatic monoesters, and combinations thereof, recovering fatty alcohol product from said liquid effluent; dehydrating the fatty alcohol product under dehydration conditions in the presence of at least one catalyst for a sufficient time and at a temperature sufficient to form an alpha-olefin product; reacting the alpha-olefin product over a heterogeneous acidic catalyst at a temperature of 100-300°C and a pressure of 0-1000 psig to form a blend of oligomers; Wherein said hydrotreating condition is basically selected according to any one in the following conditions: a reaction temperature of at least 230° C. such that the triglyceride conversion is at least 50% by weight; a reaction temperature of at least 230° C. and a total reaction pressure of 0.35-20.7 MPa gauge such that the liquid effluent has a normal paraffin concentration of at least 30% by weight; A reaction temperature of 150°C to 290°C and a total reaction pressure of 0.35 to 20.7MPa gauge, such that the liquid effluent has a fatty alcohol concentration of at least 5% by weight; A reaction temperature of 150° C. to 290° C. and a total reaction pressure of 0.35 to 20.7 MPa gauge allow the liquid effluent to have an aliphatic monoester concentration of at least 5% by weight. 52. A method for catalytically upgrading a feedstock comprising renewable materials consisting essentially of triglycerides, the method comprising: contacting the feedstock with at least one promoted catalyst selected from the group consisting of promoted self-supported catalysts, promoted supported catalysts, and combinations thereof under hydroprocessing conditions to form a liquid effluent and a gaseous product, the The catalyst comprises at least one Group VIB metal selected from molybdenum and tungsten, a Group VIII metal selected from cobalt and nickel, and the promoter is selected from substances having a spatial configuration having the following structure: Wherein x is 1 or 0, y is 1 or 0, and R ⁶ or R ⁷ is a saturated, unsaturated, cyclic, non-cyclic, branched or unbranched hydrocarbon group, wherein R ⁶ or R ⁷ is (CH) _2m (CH ₂ ) _n , wherein m and n are integers ≥ 0; the hydrotreating conditions include a temperature of 150°C-290°C and a total reaction pressure of 0.35-20.7MPa gauge pressure; recovering said liquid effluent comprising at least one of n-paraffins, fatty alcohols, aliphatic monoesters, and combinations thereof, said liquid effluent having a fatty alcohol concentration of at least 5% by weight; recovering fatty alcohol product from said liquid effluent; dehydrating the fatty alcohol product under dehydration conditions in the presence of at least one catalyst for a sufficient time and at a temperature sufficient to form an alpha-olefin product; and The alpha-olefin product is co-oligomerized with light olefins over a heterogeneous acidic catalyst at a temperature of 100-300°C and a pressure of 0-1000 psig to form a Group 3 lubricant product. 53. The method of claim 52, wherein the light olefins comprise butenes. 54. The method of claim 45, wherein the heterogeneous acidic catalyst is selected from the group consisting of acidic solid phase catalysts, acidic resin catalysts, and combinations thereof.