Process for removing chlorides from lipid raw materials using a regenerative catalyst.

Abstract

The process includes sequentially processing a set of lipid raw materials, each containing at least about 2 ppm of chloride, using a metal oxide catalyst on an oxide support, under first processing conditions in which each processed stream containing less than 1 ppm of chloride is produced from each set of lipid raw materials, until a given one of the processed streams contains more than 1 ppm of chloride and the metal oxide catalyst is replaced with a used metal oxide catalyst; converting the used metal oxide catalyst into a recycled metal oxide catalyst; and processing one or more further lipid raw materials, each containing at least about 2 ppm of chloride, using a recycled metal oxide catalyst, under second processing conditions in which one or more processed streams containing less than 1 ppm of chloride are produced.

Description

[Technical Field]

[0001] Claim of priority This application claims priority to U.S. Provisional Patent Application No. 63 / 462,300, filed on 27 April 2023, entitled “Process For Removing Chloride From Lipid Feedstocks Using Rejuvenated Catalyst,” the entire contents of which are incorporated herein by reference. [Background technology]

[0002] In the production of fuels or fuel components, such as hydrocarbons suitable for or compatible with transport fuels, there is growing interest in alternative raw materials that can replace at least a portion of crude oil. Biofuels are typically produced from raw materials derived from renewable resources, including oils and fats obtained from plants, animals, algae, and fish, as well as various wastewater, lateral line oils, and sewage sludge. These raw materials, in particular, various wastewater and lateral line oils, contain varying amounts of contaminants, such as rubber, organochlorine compounds, phospholipids and other phosphorus compounds, metals and metal compounds, and residual soaps, which can adversely affect conversion catalysts. [Overview of the Initiative]

[0003] According to an exemplary embodiment, the process is:

[0004] Multiple lipid raw materials, each containing a set of lipid raw materials with a chloride content of at least approximately 2 ppm, are sequentially treated using a metal oxide catalyst on an oxide support under a first treatment condition in which each treated stream has a chloride content of less than 1 ppm from each set of lipid raw materials, until the chloride content of one of the treated streams from each set of lipid raw materials exceeds 1 ppm and the metal oxide catalyst on the oxide support is replaced by a used metal oxide catalyst on the oxide support.

[0005] Converting used metal oxide catalysts on an oxide support into recycled metal oxide catalysts on an oxide support, and

[0006] The method includes treating one or more further lipid raw materials, each having a chloride content of at least about 2 ppm, under second treatment conditions using a regenerated metal oxide catalyst on an oxide support, which produces one or more treated streams, each having a chloride content of less than 1 ppm. [Modes for carrying out the invention]

[0007] Various exemplary embodiments described herein relate to a process for removing chlorides and other impurities from lipid raw materials using a regenerating catalyst to obtain purified lipid raw materials that can be used in oil refining.

[0008] definition

[0009] The term "lipid" is well known in this field and refers to fatty acids and their derivatives. Therefore, examples of lipids include fatty acids (both saturated and unsaturated), glycerides or glycerolipids, also called acylglycerols (e.g., monoglycerides (monoacylglycerols), diglycerides (diacylglycerols), triglycerides (triacylglycerols, TAGs, or neutral fats), phosphoglycerides (glycerophospholipids), nonglycerides (sphingolipids, sterol lipids including cholesterol and steroid hormones, prenolipids including terpenoids, fatty alcohols, waxes, and polyketides), and complex lipid derivatives (sugar-bound lipids or glycolipids, and protein-bound lipids).

[0010] The term "fatty acid" refers to a monocarboxylic acid having an aliphatic chain containing approximately 3 to 39 carbon atoms, more specifically, approximately 7 to 23 carbon atoms. The aliphatic chain may be linear or branched, and may be saturated or unsaturated (for example, it may contain one or more carbon-carbon double bonds).

[0011] The term "bio-oil" refers to a liquid product produced from biomass through a thermochemical process. Bio-oils may contain bio-derived hydrocarbon fractions, as well as oxygenated hydrocarbons such as carboxylic acids, alcohols, aldehydes, and ketones.

[0012] As used herein, the term “renewable raw materials” refers to materials derived from renewable resources (e.g., plants) rather than from geological sources. The term “renewable” is synonymous with “sustainable,” “sustainably obtained,” or “from sustainable resources.” “Geological source” means, for example, derived from crude oil, natural gas, or coal. Materials of “geological source” are not readily replenished or recycled (compared to, for example, oils derived from plants or algae).

[0013] As used herein, the terms “fresh catalyst” or “fresh metal oxide catalyst on oxide support” refer to a catalyst that has not been previously used in catalytic processes.

[0014] As used herein, the terms “spent catalyst” or “spent metal oxide catalyst on oxide support” refer to a catalyst whose chloride removal activity under the same or similar reaction conditions (e.g., temperature, pressure, inlet flow rate, etc.) is lower than when the catalyst was first used in the process. There are various possible reasons for this, but some non-limiting examples of causes of decreased chloride removal activity in a catalyst include cation or anion substitution, acidification of the catalyst surface, depletion of metal components, and / or chemical or compositional changes.

[0015] As used herein, the terms “regenerated catalyst” or “regenerated metal oxide catalyst on oxide support” refer to a catalyst that, after being used as defined above, has undergone a process to increase its chloride removal activity to a higher level than that of the used catalyst. Regenerated catalysts typically have chloride removal activity equivalent to or substantially the same as that of a fresh catalyst.

[0016] The term "hydrogenation" generally encompasses all processes in which hydrocarbon raw materials react with hydrogen in the presence of a catalyst and under hydrogenation conditions, typically at high temperature and high pressure. Hydrogenation processes include, for example, hydrogenation, hydrogenation deoxygenation, hydrogenation desulfurization, hydrogenation denitrification, hydrogenation demetallation, hydrogenation dearomaticization, hydrogenation isomerization, hydrogenation dewaxing, hydrogenation cracking, and mild hydrogenation cracking.

[0017] As used herein, the term “transport fuel” refers to fractions, cuts, or blends of hydrocarbons having a standardized distillation curve for fuels such as diesel fuel (160°C–380°C middle distillate, compliant with EN590), gasoline (40°C–210°C, compliant with EN228), aviation fuel (160°C–300°C, compliant with ASTM D-1655 jet fuel), kerosene, naphtha, etc. Liquid fuels are hydrocarbons having a standardized distillation curve for fuels such as transport fuels.

[0018] As used herein, the term "ppm" means parts per million and is a weight-relative parameter. Parts per million is micrograms per gram; for example, a component present at 10 ppm means that a specific component is present at 10 micrograms per gram of aggregate mixture.

[0019] The term "upgrading" refers to the process of transforming raw materials to possess more desirable properties.

[0020] In this specification, the term "biofuel" refers to liquid fuels derived from renewable raw materials (e.g., bio-derived raw materials).

[0021] The level of organochloride contaminants can be measured by X-ray fluorescence spectrometry, e.g., ASTM D7536-09: Standard Test Method for Chlorine in Aromatics by Monochromatic Wavelength Dispersive X-ray Fluorescence Spectrometry.

[0022] As noted above, in the production of fuels or fuel components, e.g., hydrocarbons suitable as or compatible with transportation fuels, there is increasing interest in alternative feedstocks that at least partially replace crude oil. Biofuels are typically manufactured from feedstocks derived from renewable resources. These feedstocks contain various amounts of contaminants that can negatively impact conversion catalysts.

[0023] Research and development in the processing of lipid feedstocks and the production of fuels continues, but there is still a need for improved processes to provide purified feedstocks suitable for conversion to valuable chemicals such as hydrocarbons that are substantially or completely free of chlorides at detectable levels and suitable as fuel or fuel blend components. For example, fresh catalysts effectively remove chlorides from lipid feedstocks to produce oil products that are free of chlorides at detectable levels. However, the chloride removal activity of the catalyst, which continues to remove chlorides from the lipid feedstock, gradually deteriorates over time and through the reaction / regeneration cycle, e.g., due to the accumulation of metal impurities on the catalyst over time that are not removed during coke combustion. Therefore, it is desirable to regenerate (i.e., reactivate) the chloride removal activity of the metal oxide catalyst to continue to provide purified lipid feedstocks that are substantially or completely free of chlorides at detectable levels, i.e., having a chloride content of less than 1 ppm or less than 0.5 ppm or less than 0.1 ppm.

[0024] The exemplary embodiments described herein overcome these and other drawbacks in providing an improved process for purifying renewable feedstocks by reactivating the chloride removal activity of spent metal oxide catalysts during the processing of lipid feedstocks, providing a purified renewable feedstock that contains little or no chloride in detectable amounts and is suitable for conversion to valuable chemicals. In a non-limiting, exemplary embodiment, the process comprises:

[0025] processing a plurality of lipid feedstocks, each comprising a set of lipid feedstocks each having a chloride content of at least about 2 ppm, using a metal oxide catalyst on an oxide support under a first set of processing conditions to produce a respective processed stream having a chloride content of less than 1 ppm from each of the set of lipid feedstocks, and sequentially processing until a chloride content of a given one of the respective processed streams of the set of lipid feedstocks exceeds 1 ppm and the metal oxide catalyst on the oxide support becomes a spent metal oxide catalyst on the oxide support;

[0026] converting the spent metal oxide catalyst on the oxide support to a regenerated metal oxide catalyst on the oxide support; and

[0027] processing one or more additional lipid feedstocks each having a chloride content of at least about 2 ppm using the regenerated metal oxide catalyst on the oxide support under a second set of processing conditions to produce one or more respective processed streams each having a chloride content of less than 1 ppm.

[0028] The First Processing Step

[0029] Lipid Feedstock

[0030] In step (a) of the exemplary embodiment, the lipid feedstock is derived from renewable or biological resources, and is intended herein to include feedstocks other than those obtained from mineral oil, shale oil, or coal.

[0031] In exemplary embodiments, a lipid raw material suitable for use herein may contain, for example, 0 to about 90 wt% free fatty acids, about 5 to 100 wt% fatty acid glycerol esters (e.g., monoglycerides, diglycerides, triglycerides), and 0 to about 20 wt% of one or more compounds selected from the group consisting of non-glycerol type fatty acid esters, fatty amides, and fatty alcohols. In exemplary embodiments, the lipid raw material may be combined with the earlier embodiments, but may contain more than about 50 wt% free fatty acids and fatty acid glycerol esters, such as about 70 wt% or more, for example, about 80 wt% or more, or up to 100 wt%.

[0032] In exemplary embodiments, lipid sources may include, for example, all kinds of plants, animals, and microorganisms such as algae (e.g., algal oil, algal biomass, algal cultures), fish, and lipids (e.g., fats or oils) produced by microbiological processes. In one embodiment, the lipid sources used include triglycerides.

[0033] A variety of plant-derived lipid raw materials can be used. In non-limiting exemplary embodiments, plant-derived lipid raw materials may include, for example, rapeseed oil, soybean oil (including defunged soybean oil), canola oil, cottonseed oil, grapeseed oil, mustard seed oil, corn oil, flaxseed oil, safflower oil, sunflower oil, poppy oil, pecan oil, walnut oil, oat oil, peanut oil, rice bran oil, camellia oil, castor oil, olive oil, palm oil, coconut oil, rice bran oil, algae oil, seaweed oil, and black oat oil. Other plant-derived lipid raw materials include, for example, argan, avocado, babassu palm, balanites, borneo tallow nut (Tenkawan), Brazil nut, calendula, camelina, butternut family plants, cashew nut, Chinese tallow tree (Taxus sylvatica), cocoa, coffee, kaffir lime palm, coriander, cucurbitaceae plants, euphorbia, hemp, illipe, jatropha, jojoba, kenaf, kusum (Ceylon oak), macadamia nut, mango seed, nugu (Eclipta prostrata), nutmeg, opium poppy, Lamiaceae plants, pili nut, pumpkin seed, rice bran, sacha inchi, seje ( It can be obtained from Amazon coconut, sesame, shea nuts, teased, alhambrachia, almond, daikon tallow tree, cuphea, arachnis, karanjasi seeds, neem, papaya, tonka bean, Chinese tallow tree, and ukuba, cajeput, Clausena anisata, davana, galbanum natural oleoresin, German chamomile, malaria, monarda with high geraniol content, Piperuce auritum, lupine, melissa, yarrow, ninde, patchouli, tarragon, and mugwort.

[0034] Various animal-derived lipid raw materials can also be used. In non-limiting exemplary embodiments, animal-derived lipid raw materials may include, for example, choice white grease, lard (pork fat), animal fat (beef fat), fish oil, and poultry fat.

[0035] Various lipid raw materials derived from microorganisms (eukaryotes, bacteria, and archaea) can also be used. In non-limiting exemplary embodiments, microbial lipid raw materials may include, for example, archaea, as well as L-glycerol lipids from algal oils and diatom oils. In some embodiments, microbial lipid raw materials may include bacteria, protozoa, algae, and fungi.

[0036] In some embodiments, lipid raw materials derived from both plant and animal sources can be used, such as yellow grease, white grease, and brown grease. In non-limiting exemplary embodiments, yellow, white, or brown grease may include frying oil from a frying pan and thus may contain fats derived from both plants and animals. Specifically, the lipid raw material may include waste cooking oil. Brown grease (also known as trap grease) may include fat extracted from a sewage system and therefore may contain fats derived from both plants and animals. In some embodiments, the lipid raw materials used in the embodiments may include abiotic lipid raw materials. Black oil may also be included as a lipid raw material in the present invention.

[0037] In non-limiting exemplary embodiments, lipid raw materials include raw materials derived from low-value renewable waste, lateral line oil, by-products, refining waste and residues, sewage sludge, and combinations thereof.

[0038] In non-limiting exemplary embodiments, the lipid raw material may be selected from the group consisting of acid soap stock, fatty acid distillates obtained by physically refining vegetable oil or animal fat, distilled corn oil (DCO) obtained in the production of ethanol, waste cooking oil, lard, brown grease, yellow grease, trap grease, waste fat, lower oil, supercritical water liquefied oil (SCWL oil), vegetable oil, animal fat, and any combination thereof.

[0039] In exemplary embodiments, the lipid raw material may be combined with one or more of the elements described in the preceding paragraphs, but it contains one or more of the alkali metals, alkaline earth metals, and / or other metals such as iron and manganese, each of which has catalytic poisoning properties and is therefore often considered unsuitable for catalytic treatment in the purification process, even in small amounts. Alkali metals, alkaline earth metals, and other metals may typically include Na, K, Mg, Ca, Mn, Fe, or combinations thereof. The lipid raw material may contain alkali metals, alkaline earth metals, metals of groups VIIB and VIIIB, or combinations thereof, calculated as elemental metals, in total at least about 1 ppm (e.g., about 1 to about 250 ppm, about 1 to about 100 ppm, about 1 to about 50 ppm, about 1 to about 25 ppm, about 2 to about 250 ppm, about 2 to about 100 ppm, or about 2 to about 25 ppm). The total metal content can be measured using the AOCS recommended procedure Ca 17-01.

[0040] In non-limiting exemplary embodiments, lipid raw materials may include low-value lipid raw materials, such as various types of animal fats and waste oils, which generally have a relatively high concentration of free fatty acids. One method for evaluating the concentration of free fatty acids is to measure the total acid value (TAN) of the raw material. The total acid value is expressed in milligrams as the amount of potassium hydroxide (KOH) required to neutralize 1 gram of the chemical substance being evaluated.

[0041] In exemplary embodiments, the lipid raw material may be combined with one or more of the preceding paragraphs, but the total acid value may be at least about 5 mg KOH / g (e.g., about 5 to about 150 mg KOH / g, about 10 to about 150 mg KOH / g, about 10 to about 100 mg KOH / g, about 10 to about 50 mg KOH / g, about 10 to about 25 mg KOH / g, or about 10 to about 20 mg KOH / g). The total acid value can be measured using ASTM D664.

[0042] Lipid raw materials typically contain various amounts of impurities, such as phosphorus, silicon, chlorides, alkali metals, alkaline earth metals, and other metals. In exemplary embodiments, the lipid raw material may contain chlorides in various amounts, such as at least about 2 ppm, or at least about 4 ppm, or at least about 10 ppm (e.g., about 2 to about 100 ppm, about 2 to about 75 ppm, about 2 to about 50 ppm, about 10 to about 100 ppm, or about 10 to about 50 ppm), and any combination of any of these lower and upper limits.

[0043] In non-limiting embodiments, in addition to lipid raw materials with a chloride content of at least about 2 ppm, further lipid raw materials with a chloride content of less than 2 ppm may be present during processing. In other embodiments, in addition to lipid raw materials with a chloride content of at least about 2 ppm, further lipid raw materials that do not contain chloride may be present during processing.

[0044] In exemplary embodiments, the lipid raw material may be pretreated. Suitable pretreatments include, but are not limited to, degumming, neutralization, bleaching, deodorization, or any combination thereof.

[0045] catalyst

[0046] The catalyst used in step (a) is a fresh metal oxide catalyst on an oxide support. Suitable metals for the metal oxide include, for example, Na, K, Mg, Ca, Sr, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, rare earth metals, or mixtures thereof. In exemplary embodiments, the metal oxide may be present in an amount ranging from about 0.1 to about 10 wt%. In exemplary embodiments, the suitable oxide support can be any suitable inorganic oxide support. Representative examples of such suitable oxide supports include, but are not limited to, alumina, silica, silica-alumina, titania, zirconia, or mixtures thereof. In one embodiment, the oxide support is one of alumina and silica-alumina, and if it is a silica-alumina support, the silica content can be in the range of about 2 to about 30 wt%. The alumina can be any alumina that has been conventionally used as a hydrogenation catalyst. Such alumina is typically porous amorphous alumina with an average pore size of about 50 to about 200 angstroms. In non-limiting exemplary embodiments, the metal oxide catalyst comprises CaO and the oxide support is alumina. However, this embodiment is merely illustrative, and this specification assumes any combination of the aforementioned metal oxides and oxide supports.

[0047] The metal oxide catalyst may be any catalyst form commonly used in this field, such as spherical, granular, pelletized, chipped, ring-shaped, extruded, or powdered.

[0048] Processing of lipid raw materials

[0049] The lipid raw materials are sequentially processed using a metal oxide catalyst on an oxide support under processing conditions that generate a liquid fraction containing bio-oil and a treated stream containing the metal oxide catalyst, each fraction having a lower content of free fatty acids and impurities than the respective starting lipid raw materials. The resulting bio-oil, after further processing described later, becomes a renewable raw material particularly suitable for hydrogenation in biofuel production.

[0050] While not bound by theory, the process is thought to proceed by a thermochemical process involving one or more of the following reactions: cracking, decarboxylation, decarboxylation coupling, dehydration, and / or deoxygenation.

[0051] In exemplary embodiments, the conditions suitable for processing lipid raw materials may be combined with one or more of the conditions in the preceding paragraph, but include a temperature in the range of about 400°C to about 700°C (e.g., about 425°C to about 650°C, or about 450°C to about 600°C), a pressure in the range of 0 to about 10 MPa (e.g., about 0.1 to about 5 MPa, or about 0.1 to about 1 MPa), and about 0.1 to about 10 hours. -1 Liquid space velocity (LHSV) in the range of (e.g., approximately 0.2 to approximately 5h) -1 , or approximately 0.3 to 3 hours -1 It may include one or more of the following. A combination of any of the lower and upper limits above is also possible.

[0052] The treatment of lipid feedstocks using metal oxide catalysts may be carried out in the presence of a carrier gas. Suitable carrier gases include, for example, hydrogen, nitrogen, carbon dioxide, H2O (water vapor), or C1-C4 hydrocarbons (e.g., methane, ethane, propane, or mixtures thereof). These gases may be mixed in the reaction mixture of the lipid feedstock and the metal oxide catalyst, and / or formed during the reaction. The carrier gas may be used to remove gases or volatile reaction products such as carbon dioxide (CO2) and H2O (water vapor) from the mixture of products.

[0053] The treatment of lipid raw materials using metal oxide catalysts may be carried out in any reactor or reactor configuration, provided it is appropriate. Suitable reactors or reactor configurations include, for example, fixed-bed reactors, moving-bed reactors, slurry reactors, fluidized-bed reactors, boiling-bed reactors, transport-bed reactors, two-phase reactors, riser reactors, and batch reactors. The lipid raw material feed stream can be flowed over the catalyst bed as an upflow or downflow in either a liquid, vapor, or mixed-phase state.

[0054] The process can be batch-based, semi-batch-based, or continuous, but a continuous process is preferable.

[0055] As those skilled in the art will understand, the process first involves treating a first lipid raw material having a chloride content of at least about 2 ppm under first treatment conditions, using a fresh metal oxide catalyst on an oxide support, to produce a first treated stream containing a liquid fraction including bio-oil, which has a lower chloride content than the starting material of the first lipid raw material, for example, the chloride content of the first treated stream is less than 1 ppm, or about 0.5 ppm, or about 0.01 ppm, or about 0.001 ppm, or the chloride content is 0 ppm.

[0056] Next, the process continues by treating a second lipid raw material having a chloride content of at least about 2 ppm with a metal oxide catalyst on the same oxide support used for treating the first lipid raw material, under second treatment conditions, which produce a second treated stream containing a liquid fraction including bio-oil with a lower chloride content than the starting material of the second lipid raw material, for example, the chloride content of the second treated stream is less than 1 ppm, or about 0.5 ppm, or about 0.01 ppm, or about 0.001 ppm, or the chloride content is 0 ppm.

[0057] The process continues by sequentially treating further lipid raw materials having a chloride content of at least about 2 ppm, each with a metal oxide catalyst on the same oxide support, under respective treatment conditions that produce treated flows with a chloride content of less than 1 ppm, or about 0.5 ppm, or about 0.01 ppm, or about 0.001 ppm, respectively. As will be readily apparent to those skilled in the art, the process can also be sequentially treated with the aforementioned further lipid raw materials having a chloride content of less than 2 ppm, each with the same metal oxide catalyst on the oxide support, under respective treatment conditions that produce treated flows.

[0058] The process continues until the chloride content of one of the treated streams exceeds 1 ppm and the metal oxide catalyst on the oxide support is replaced by a used metal oxide catalyst on the oxide support. In other words, as described above, the ability of the metal oxide catalyst to remove impurities such as chlorides from lipid raw materials can gradually deteriorate over time and throughout the reaction / regeneration cycle. Therefore, if the chloride removal activity of the metal oxide catalyst reaches a stage where it can only remove less than 1 ppm of chloride from the lipid raw material being treated, the metal oxide catalyst is partially inactivated. Conventionally, such an inactivated catalyst was no longer active enough to obtain the desired chloride removal efficiency and had to be replaced with a fresh catalyst; that is, it had to be removed and discarded and refilled with a fresh metal oxide catalyst. However, it has been found that it is possible to promote the chloride removal activity of the catalyst and restore or regenerate its removal activity, thereby eliminating the need to discard the catalyst and replace it with a fresh catalyst. Furthermore, the regeneration of dechlorination activity can be achieved in situ within the reactor without removing the catalyst.

[0059] The resulting treated streams, each containing a liquid fraction with bio-oil, may contain alkali metals, alkaline earth metals, metals from groups VIIB and VIIIB of the periodic table (other metals), or combinations thereof, in total less than about 1 ppm, preferably less than about 0.5 ppm, as calculated elemental metals.

[0060] The resulting treated streams, each containing a liquid fraction with bio-oil, may have a TAN of less than 5 mgKOH / g (e.g., less than 4 mgKOH / g, less than 3 mgKOH / g, less than 2 mgKOH / g, or less than 1 mgKOH / g).

[0061] The bio-oil(s) obtained from the aforementioned processing steps, after further processing as described later, becomes a renewable raw material particularly suitable for hydrogenation in biofuel production.

[0062] Catalyst regeneration process

[0063] Each lipid raw material is treated with a metal oxide catalyst and an oxide support, and as a result, a treated stream is produced that includes a liquid fraction containing bio-oil along with the spent metal oxide catalyst on the oxide support. Then, the spent metal oxide catalyst on the oxide support is converted into a regenerated metal oxide catalyst on the oxide support that has chloride removal activity equivalent to or substantially the same as that of the fresh catalyst.

[0064] In one non-limiting exemplary embodiment, a spent metal oxide catalyst can be converted into a regenerated metal oxide catalyst by directly spraying a solution of a water-soluble metal salt onto the spent metal oxide catalyst. For example, a metal such as calcium can be added in the form of a solution of a water-soluble calcium salt, such as calcium acetate, which is then sprayed directly onto the spent metal oxide catalyst. The solution of the water-soluble metal salt can be sprayed onto the spent metal oxide catalyst using any known suitable spraying apparatus. Suitable metal salts, such as calcium salts, include those that change to calcium carbonate, calcium oxide, or calcium hydroxide under reaction conditions. Representative examples of suitable calcium salts include, but are not limited to, calcium nitrate, calcium hydroxide, calcium acetate, or other calcium carboxylates. As will be readily apparent to those skilled in the art, other metals such as magnesium and barium can also be considered and used in place of calcium, and can be deposited in a similar manner.

[0065] In exemplary embodiments, a spent metal oxide catalyst can be converted into a regenerated metal oxide catalyst without removing it from the reactor system. For example, in non-limiting exemplary embodiments, a concentrated metal (e.g., calcium) salt solution can be sprayed onto the spent metal oxide catalyst until a desired amount of metal is added. The reactor is then heated to a suitable drying temperature for moisture removal (e.g., about 120°C to about 200°C), then to a calcination temperature, and finally to a suitable reaction temperature such as about 400°C to about 600°C to dry the sprayed metal oxide catalyst. The metal salt, such as calcium acetate, decomposes under reaction conditions to form the corresponding calcium carbonate or calcium oxide. The desired amount of metal added to the spent metal oxide catalyst can be sufficient to convert the spent metal oxide catalyst on the oxide support into a regenerated metal oxide catalyst on the oxide support. For example, the desired amount of metal added to the spent metal oxide catalyst can be about 0.1 to about 10 wt%.

[0066] In exemplary embodiments, a used metal oxide catalyst can be converted into a regenerated metal oxide catalyst by injecting a metal salt, such as a calcium salt, magnesium salt, or barium salt, into the metal oxide catalyst along with the lipid raw material when treating the lipid raw material with the metal oxide catalyst on an oxide support. In embodiments, the metal salt in this case may be mixed with the lipid raw material as an emulsion of an aqueous solution of the metal salt, such as calcium acetate, in an oil feed. In alternative embodiments, an oil-soluble form of the salt may be dissolved in oil. Typical examples of oil-soluble salts include acetylacetonate salts, which are known to be soluble in organic solvents. For example, calcium acetylacetonate is known to be highly soluble in low molecular weight alcohols such as methanol and ethanol.

[0067] Therefore, in one embodiment, a solution containing an oil-soluble metal salt in a low molecular weight alcohol can be injected into the lipid feedstock stream in an amount such that the metal is about 0.05 to about 5 wt%. In one embodiment, glycerin may be used as a solvent for the oil-soluble metal salt. In another alternative embodiment, the mixture in the feedstock contains small amounts of calcium or magnesium, which are known to be impurities in some low-value lipid feedstocks. The injection of the metal salt together with the lipid feedstock can be carried out in reactor configurations such as moving bed or fluidized bed reactors, in which, unlike the fixed bed method, more of the catalyst inventory comes into contact with the new feedstock over time.

[0068] Second processing step

[0069] After converting the used metal oxide catalyst on the oxide support into a regenerated metal oxide catalyst on the oxide support having chloride removal activity equivalent to or substantially similar to that of the fresh metal oxide catalyst, the process continues by sequentially treating at least one or more further lipid raw materials having a chloride content of at least about 2 ppm with the regenerated metal oxide catalyst on the oxide support under the above-described treatment conditions, each resulting in a treated stream containing a liquid fraction with bio-oil having a lower chloride content than the starting material of the lipid raw material, for example, the chloride content of each treated stream being less than 1 ppm, or about 0.5 ppm, or about 0.01 ppm, or about 0.001 ppm, or 0 ppm.

[0070] As described above, in addition to lipid raw materials with a chloride content of at least about 2 ppm, further lipid raw materials with a chloride content of less than 2 ppm may be present during this processing step. In other embodiments, in addition to lipid raw materials with a chloride content of at least about 2 ppm, further lipid raw materials that do not contain chloride may also be present during processing.

[0071] The process then continues by sequentially treating additional lipid raw materials, each with a recycled metal oxide catalyst on the same oxide support, under different treatment conditions that produce treated streams with a chloride content of less than 1 ppm, less than approximately 0.5 ppm, less than approximately 0.01 ppm, less than approximately 0.001 ppm, or 0 ppm. The process continues, again as described above, until the chloride content of one of the treated streams exceeds 1 ppm and the metal oxide catalyst on the oxide support is replaced by a used metal oxide catalyst on the oxide support.

[0072] The resulting bio-oil(s)(s) become a renewable raw material particularly suitable for hydrogenation in biofuel production after further processing described later.

[0073] Hydrogenation

[0074] The bio-oil produced by the processes of the exemplary embodiments disclosed herein is beneficial in that it can be used directly as a refining raw material. The resulting bio-oil can be mixed with one or more mineral oil raw materials derived from crude oil, shale oil, or coal and used in the same way as a refining raw material.

[0075] If necessary, a catalytic hydrogenation process may be performed on the bio-oil. At least one of the resulting effluents (hydrogenation products) may be fractionally distilled in a fractional distillation process to obtain hydrocarbon fractions suitable as renewable fuels or fuel components, and useful as transport fuels, fuel components, and other chemicals. The catalytic hydrogenation process may be carried out in one step or in multiple steps.

[0076] In the catalytic hydrogenation process, one or more fractions of the bio-oil (such as distillation cuts) may be treated individually, or the entire bio-oil may be treated together.

[0077] The catalytic hydrogenation treatment may include at least a hydrodeoxygenation step. The catalytic hydrogenation treatment may include one or more steps selected from a hydroisomerization step and a hydrocracking step after the hydrodeoxygenation step.

[0078] The hydrogenation treatment can be carried out using one or more hydrogenation treatment catalysts containing one or more metals selected from Group VIA and Group VIII metals. Particularly useful ones are, for example, Mo, W, Co, Ni, Pt, and Pd. Also, the catalyst(s) may contain one or more carrier materials, such as zeolite, alumina, alumina-silica, zirconia, alumina-silica-zeolite, and activated carbon. A mixture of CoO and MoO3 (CoMo), and / or a mixture of NiO and MoO3 (NiMo), and / or a mixture of Ni, Mo, and Co and / or NiW, and one or more carrier materials selected from zeolite, alumina, silica, zeolite-alumina, alumina-silica, alumina-silica-zeolite, and activated carbon are suitable. Also, noble metals such as Pt and / or Pd dispersed on alumina may be used.

[0079] The hydrogenation treatment conditions include a temperature of about 100°C to about 450°C (for example, about 200°C to about 370°C, or about 230°C to about 350°C), a pressure of about 0.5 to about 30 MPa (for example, about 3 to about 25 MPa, or about 3 to about 12 MPa), a liquid hourly space velocity of about 0.01 to about 10 h -1 (for example, about 0.1 to about 5 h -1 ). The hydrogen gas treatment rate can be in the range of about 600 to about 4000 Nm 3 / m 3 (for example, about 1300 to about 2200 Nm 3 / m 3 ).

[0080] Hydrogenation is carried out in a reaction phase. The reaction phase may include one or more reactors or reaction zones, each containing one or more catalyst beds composed of the same or different catalysts. Fixed beds are preferred, but other types of catalyst beds / reactors can also be used. Such other types of catalyst beds include fluidized beds, boiling beds, slurry beds, and moving beds. Interstage cooling or heating can be used between reactors, between reaction zones, or between catalyst beds within the same reactor.

[0081] From the final reactor, at least one effluent from the hydrogenation treatment is discharged. In one embodiment, the effluent is sent to a separator, such as a suitable separator or flushing device. In the separator, a gaseous stream, typically containing water, hydrogen, light hydrocarbons (e.g., C1-C5 hydrocarbons), H2S, CO, and CO2, is separated from a liquid component containing hydrocarbons beyond C5 and some C1-C5 hydrocarbons. The water and gas may be separated by other means well known to those skilled in the art.

[0082] The liquid hydrocarbon stream obtained from the hydrogenation process contains fuel hydrocarbons with a maximum boiling point of 380°C, in accordance with ISO EN3405. Those skilled in the art can obtain any suitable hydrocarbon product that boils appropriately within the range of transport fuels by changing the distillation conditions and, if necessary, the cut-off point temperature.

[0083] The following exemplary embodiments are intended to be non-limiting.

[0084] In the following examples, the chloride content is expressed in ppm of chloride relative to the weight of the raw material or the weight of the composition, and is measured by X-ray fluorescence using the Chlora R benchtop analyzer from XOS. [Examples]

[0085] A 3 / 4-inch reactor was filled with 50 ml of calcium-doped alumina catalyst, and then, as described below, lipid (oil) raw materials were flowed upflow over the calcium-doped alumina catalyst in the presence of vapor at a vapor / oil raw material weight ratio of 1:1, temperature of 900°F, atmospheric pressure, and oil flow rate of approximately 30-40 g / hour, and runs 1-3 were performed. In the first run, 6 kg of pre-treated waste cooking oil (UCO) raw material containing 11 ppm of chloride was processed. In the second run, using the same batch of filled catalyst, 10 kg of chloride-free soybean oil raw material was processed. In neither run 1 nor run 2 was chloride detected in the oil product. In the third run, using the same batch of filled catalyst, 1 kg of untreated UCO raw material with a chloride content of 4.6 ppm was processed. Samples of the oil product from run 3 were found to contain chloride at various concentrations, up to a maximum of 1.8 ppm.

[0086] At this point, the calcium-doped alumina catalyst was cooled, and a solution of 5 g of calcium acetate dissolved in 30 ml of water was poured onto the catalyst bed, which remained filled in the reactor. The calcium-doped alumina catalyst was then gradually heated to 900°F in nitrogen and returned to operating condition. Next, in the fourth run, 10 kg of untreated UCO feedstock with a chloride content of 4.6 ppm was treated under the conditions described above. No chloride was detected in the product treated after calcium was added to the calcium-doped alumina catalyst.

[0087] According to one aspect of this disclosure, the process is

[0088] (a) Multiple lipid raw materials, each containing a set of lipid raw materials having a chloride content of at least about 2 ppm, are sequentially treated with a metal oxide catalyst on an oxide support under first treatment conditions in which each treated stream containing less than 1 ppm of chloride is produced from each set of lipid raw materials, until the chloride content of one given stream from each set of lipid raw materials exceeds 1 ppm and the metal oxide catalyst on the oxide support is replaced by a used metal oxide catalyst on the oxide support.

[0089] (b) Converting spent metal oxide catalysts on oxide supports into recycled metal oxide catalysts on oxide supports,

[0090] (c) The process involves treating one or more further lipid raw materials, each having a chloride content of at least about 2 ppm, under second processing conditions using a regenerated metal oxide catalyst on an oxide support, to produce one or more treated streams, each having a chloride content of less than 1 ppm.

[0091] In one or more further exemplary embodiments, which may be combined with the preceding paragraphs, the multiple lipid raw materials and one or more further lipid raw materials independently include at least one fatty acid selected from the group consisting of acid soap stock, fatty acid distillates obtained by physically refining vegetable oil or animal fat, distilled corn oil obtained in the production of ethanol, waste cooking oil, lard, brown grease, yellow grease, trap grease, waste fat, lower oil, supercritical water liquefied oil, vegetable oil, animal fat, and any combination thereof.

[0092] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, sequentially treating a plurality of lipid raw materials with a metal oxide catalyst on an oxide support under first treatment conditions includes: (i) treating one or more first lipid raw materials with a metal oxide catalyst under first treatment conditions that produce a first treated stream with a chloride content of less than 1 ppm; (ii) treating one or more second lipid raw materials with a metal oxide catalyst under first treatment conditions that produce a second treated stream with a chloride content of less than 1 ppm; (iii) treating one or more third lipid raw materials with a metal oxide catalyst under first treatment conditions that produce a third treated stream with a chloride content of less than 1 ppm; and (iv) treating one or more fourth lipid raw materials with a metal oxide catalyst under first treatment conditions that produce a fourth treated stream with a chloride content of more than 1 ppm.

[0093] In one or more further exemplary embodiments, the first and second processing conditions may be combined with the preceding paragraphs, but independently, the first and second processing conditions are a temperature in the range of about 400°C to about 700°C, a pressure in the range of about 0.1 to about 10 MPa, and about 0.1 to about 10 h -1 It includes one or more of the liquid space velocities within the range.

[0094] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, the metal oxide catalyst comprises a metal selected from the group consisting of Na, K, Mg, Ca, Ba, Sr, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, rare earth metals, and any combination thereof, and the oxide support is selected from the group consisting of alumina, silica, silica-alumina, titania, zirconia, and any combination thereof.

[0095] In one or more further exemplary embodiments, the metal oxide catalyst may be combined with the preceding paragraphs, but the metal oxide catalyst comprises a metal selected from the group consisting of Ca, Mg, Ba, and any combination thereof.

[0096] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, the metal oxide catalyst comprises CaO and the oxide support comprises alumina.

[0097] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, converting a spent metal oxide catalyst on an oxide support to a regenerated metal oxide catalyst on an oxide support involves contacting the spent metal oxide catalyst with a solution containing a water-soluble metal salt.

[0098] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, the metal in the water-soluble metal salt is one of calcium, magnesium, or barium.

[0099] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, contacting a spent metal oxide catalyst with a solution containing a water-soluble metal salt involves spraying the spent metal oxide catalyst with a solution containing one of calcium nitrate, calcium hydroxide, calcium acetate, or calcium carboxylate, wherein the spent metal oxide catalyst contains CaO.

[0100] In one or more further exemplary embodiments, step (a) may be combined with the preceding paragraph, but the step (a) is carried out within the reactor system, and the step of converting the spent metal oxide catalyst on the oxide support to a regenerated metal oxide catalyst on the oxide support is carried out without removing the spent metal oxide catalyst from the reactor system.

[0101] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, converting a spent metal oxide catalyst on an oxide support to a regenerated metal oxide catalyst on an oxide support involves spraying a solution containing a water-soluble metal salt onto the spent metal oxide catalyst on the oxide support and heating the reactor.

[0102] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, the solution containing the water-soluble metal salt is a calcium acetate solution, and the spent metal oxide catalyst contains CaO.

[0103] In one or more further exemplary embodiments, the processes of steps (a) and (c) may be carried out under a carrier gas flow, in combination with the preceding paragraphs.

[0104] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, the carrier gas is nitrogen, carbon dioxide, C1-C4 hydrocarbons, water, or a mixture thereof.

[0105] In one or more further exemplary embodiments, the multiple lipid raw materials and one or more further lipid raw materials may be used independently, in combination with the preceding paragraph.

[0106] (i) The total acid value measured by ASTM D664 is at least about 5 mg KOH / g,

[0107] (ii) The chloride content is approximately 2 ppm to approximately 100 ppm, exhibiting at least one of these characteristics.

[0108] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, the process further comprises fractional distillation of each treated stream from step (a) and one or more of each treated stream from step (c) to obtain a gaseous fraction and a liquid fraction containing bio-oil.

[0109] In one or more further exemplary embodiments, the process may be combined with the preceding paragraphs, further comprising a catalytic hydrogenation step for the bio-oil to obtain a hydrogenation product.

[0110] In one or more further exemplary embodiments, the catalytic hydrogenation treatment may be combined with the preceding paragraphs, but includes a hydrogenation deoxygenation step.

[0111] In one or more further exemplary embodiments, which may be combined with the preceding paragraph, each treated stream in step (a) and at least one of each of the one or more treated streams in step (c) have a chloride content of 0.

[0112] The various features disclosed herein are described in the context of a single embodiment for the sake of brevity, but may be provided individually or in any subcombination where appropriate. All combinations of embodiments are specifically encompassed in the exemplary embodiments disclosed herein, and every possible combination is deemed to be individually and explicitly disclosed. Similarly, all subcombinations described in embodiments illustrating such variables are specifically encompassed in this configuration, and every possible such subcombination is disclosed herein as individually and explicitly disclosed.

[0113] While the above description contains many details, these details should be interpreted not as limiting the invention, but merely as examples of preferred embodiments. Those skilled in the art will likely conceive of many other embodiments within the scope and spirit of the invention as defined by the claims appended herein.

Claims

1. (a) Multiple lipid raw materials, each containing a set of lipid raw materials having a chloride content of at least about 2 ppm, are sequentially treated using a metal oxide catalyst on an oxide support under first treatment conditions in which each treated stream containing less than 1 ppm of chloride is generated from the set of lipid raw materials, until the chloride content of one given stream from each of the set of lipid raw materials exceeds 1 ppm and the metal oxide catalyst on the oxide support is replaced by a used metal oxide catalyst on the oxide support. (b) Converting the used metal oxide catalyst on the oxide carrier into a regenerated metal oxide catalyst on the oxide carrier, (c) A process comprising treating one or more further lipid raw materials, each having a chloride content of at least about 2 ppm, using the recycled metal oxide catalyst on the oxide carrier, under second treatment conditions, which produce one or more treated streams, each having a chloride content of less than 1 ppm.

2. The process according to claim 1, wherein the plurality of lipid raw materials and the one or more further lipid raw materials independently include at least one fatty acid selected from the group consisting of acid soap stock, fatty acid distillates obtained by physically refining vegetable oil or animal fat, distilled corn oil obtained in the production of ethanol, waste cooking oil, lard, brown grease, yellow grease, trap grease, waste fat, lower oil, supercritical water liquefied oil, vegetable oil, animal fat, and any combination thereof.

3. The process according to claim 1 or 2, wherein sequentially treating a plurality of lipid raw materials under first processing conditions using the metal oxide catalyst on the oxide support comprises: (i) treating one or more first lipid raw materials under first processing conditions using the metal oxide catalyst to generate a first treated stream having a chloride content of less than 1 ppm; (ii) treating one or more second lipid raw materials under first processing conditions using the metal oxide catalyst to generate a second treated stream having a chloride content of less than 1 ppm; (iii) treating one or more third lipid raw materials under first processing conditions using the metal oxide catalyst to generate a third treated stream having a chloride content of less than 1 ppm; and (iv) treating one or more fourth lipid raw materials under first processing conditions using the metal oxide catalyst to generate a fourth treated stream having a chloride content of more than 1 ppm.

4. The first and second processing conditions are, independently, a temperature in the range of about 400°C to about 700°C, a pressure in the range of about 0.1 to about 10 MPa, and about 0.1 to about 10 hours. －１ The process according to any one of claims 1 to 3, comprising one or more liquid space velocities within the range of .

5. The process according to any one of claims 1 to 4, wherein the metal oxide catalyst comprises a metal selected from the group consisting of Na, K, Mg, Ca, Ba, Sr, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, rare earth metals, and any combination thereof, and the oxide support is selected from the group consisting of alumina, silica, silica-alumina, titania, zirconia, and any combination thereof.

6. The process according to one of claims 1 to 4, wherein the metal oxide catalyst comprises a metal selected from the group consisting of Ca, Mg, Ba, and any combination thereof.

7. The process according to one of claims 1 to 4, wherein the metal oxide catalyst comprises CaO and the oxide support comprises alumina.

8. The process according to one of claims 1 to 7, wherein the conversion of the spent metal oxide catalyst on the oxide support to a regenerated metal oxide catalyst on the oxide support comprises contacting the spent metal oxide catalyst with a solution containing a water-soluble metal salt.

9. The process according to claim 8, wherein the metal in the water-soluble metal salt is one of calcium, magnesium, or barium.

10. The process according to claim 8, wherein contacting the spent metal oxide catalyst with a solution containing a water-soluble metal salt comprises spraying the spent metal oxide catalyst with a solution containing one of calcium nitrate, calcium hydroxide, calcium acetate, or calcium carboxylate, the spent metal oxide catalyst contains CaO.

11. The process according to one of claims 1 to 10, wherein step (a) is carried out within a reactor system, and the conversion of the spent metal oxide catalyst on the oxide support to the regenerated metal oxide catalyst on the oxide support is carried out without removing the spent metal oxide catalyst from the reactor system.

12. The process according to claim 11, wherein the conversion of the spent metal oxide catalyst on the oxide support to the regenerated metal oxide catalyst on the oxide support comprises spraying a solution containing a water-soluble metal salt onto the spent metal oxide catalyst on the oxide support and heating the reactor.

13. The process according to claim 12, wherein the solution containing the water-soluble metal salt is a calcium acetate solution, and the used metal oxide catalyst contains CaO.

14. The process according to one of claims 1 to 13, wherein the processing in step (a) and step (c) is carried out under a flow of carrier gas.

15. The carrier gas is nitrogen, carbon dioxide, C １ ~C ４ The process according to claim 14, wherein the process is a hydrocarbon, water, or a mixture thereof.

16. The plurality of lipid raw materials and the one or more further lipid raw materials are independently, (i) The total acid value measured by ASTM D664 is at least about 5 mg KOH / g, (ii) The process according to one of claims 1 to 15, wherein the chloride content is at least one of the properties of about 2 ppm to about 100 ppm.

17. The process according to one of claims 1 to 16, further comprising fractional distillation of each of the treated streams in step (a) and one or more of the treated streams in step (c) to obtain a gas fraction and a liquid fraction containing bio-oil.

18. The process according to claim 17, further comprising a catalytic hydrogenation step of the bio-oil to obtain a hydrogenation product.

19. The process according to claim 18, wherein the catalytic hydrogenation treatment includes a hydrogenation deoxygenation step.

20. The process according to one of claims 1 to 19, wherein at least one of the treated streams in step (a) and the one or more treated streams in step (c) has a chloride content of 0.

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