JP5690734B2 - Co-processing diesel with vegetable oil to produce a low cloud point hybrid diesel biofuel - Google Patents

Description

  The present invention relates generally to methods and systems for efficiently producing low sulfur hybrid diesel biofuels by co-processing diesel fuels, particularly blends of petroleum diesel and vegetable or cereal oil.

Biofuels are (1) they are renewable resources, (2) their production is less dependent on geographical circumstances, (3) they are a direct replacement for petroleum-based fuels in existing means of transportation providing the possibility of, and (4) biofuel precursors - particularly for a number of reasons, including the fact, that can substantially reduce the greenhouse gas emissions of the net for the CO ₂ uptake by cellulosic material In addition, interest is increasing. “Fuels Gold,” New Scientist, 23 September, pp. 19 36-41, 2006.

  Easily obtained biofuels are vegetable oils mainly containing triglycerides and some free fatty acids. However, the nature of vegetable oils is that the viscosity of vegetable oils is generally too high so that they do not burn enough to produce pollutants, thereby leaving harmful carbon deposits in the engine, which is then It is generally unsuitable for use as a direct alternative to petroleum diesel. In addition, vegetable oils tend to gel on the cold side, thus preventing their use in cold climates. These problems are alleviated when vegetable oils are blended with petroleum fuels, but still remain an obstacle to long-term use in diesel engines. Pearce, 2006; Huber et al., “(Transport Fuel Synthesis from Biomass: Chemistry, Catalysts and Engineering) Synthesis of Transportation Fuels Biomass: Chemistry, Catalysts, and Engineering” Chem. Rev. , Vol. 106, pp. See 4044-4098, 2006.

  Transesterification is a method currently used to convert vegetable oils to diesel compatible fuels (ie, general purpose biodiesel) that can be combusted in general purpose diesel engines. However, low temperature flow problems similar to general purpose biodiesel fuels remain. This problem is due, at least in part, to the fact that general purpose biodiesel often becomes viscous and does not flow easily at lower temperatures, for example near the solidification temperature (about 0 ° C.). Therefore, the limit of biodiesel produced by this method is generally that it has a higher cloud point (and pour point), which makes it unusable in some specific cold climates It becomes.

  An alternative to the above transesterification, as described herein, is to mix a vegetable oil (eg, canola oil) with a universal diesel to form a mixture, and then hydrotreat the mixture to obtain a hybrid diesel biofuel. That is. In general, vegetable oils are present in the mixture in lower amounts than general purpose diesel. Depending on the embodiment, the vegetable oil typically comprises about 10 weight percent of the mixture.

When vegetable oil is added to diesel going to the hydrotreater, the cloud point typically increases, driving the diesel “out of specification”. This requires readjustment of the diesel cut point, thereby reducing yield. The prior art teaches an isomerization dewaxing catalyst that lowers the cloud point, which requires removal of H ₂ S and NH ₃ from the hydrotreater effluent prior to the dewaxing reactor, otherwise For example, the dewaxing catalyst must be operated at a high temperature which shortens the service life. Therefore, there is still a great need for a method that can economically utilize biomass in the production of hydrotreated diesel fuel while maintaining a relatively low cloud point, which would be very beneficial.

  In some embodiments, the present invention is directed to methods (ie, processes) and systems that co-process vegetable oil and petroleum diesel to obtain a hybrid diesel product containing biomass-derived components. Typically, such methods and systems operate to provide a hybrid diesel product that benefits from (partially) biomass-derived components without the poor low temperature properties of commodity ester biodiesels.

To refer to at least some of the above limitations and / or recognized needs for biofuels and / or their processing, in some embodiments, the present invention provides the following method—vegetable oil and petroleum. A low cloud point hybrid (bio) diesel product that is partly biomass derived by first hydrotreating a mixture of diesel to obtain a sulfur-reduced hybrid intermediate and then treating the hybrid intermediate with an isomerization unit Oriented to a method for obtaining Ideally, the low cloud point hybrid diesel product has a cloud point within (or at least close to) that of standard diesel. Typically, such embodiments utilize sulfur and / or nitrogen tolerant isomerization catalysts that do not typically remove H ₂ S and NH ₃ from the hybrid intermediate stream prior to isomerization. Due to its intermediate removal of H ₂ S and NH ₃ , such sulfur and / or nitrogen tolerant isomerization catalysts allow favorable economics of such methods / systems. Such isomerization catalysts are described in Miller US patent application Ser. No. 12 / 181,652, incorporated herein by reference.

In some embodiments, the present invention is directed to one or more methods for producing a hybrid diesel (bio) fuel product, such methods, a) a combination with diesel vegetable oil Forming a mixture, wherein the vegetable oil comprises 10 weight percent or less of the first mixture, b) hydrotreating the first mixture to obtain a second mixture, the first mixture The triglyceride component of is deoxygenated and at least 95 atomic percent of the sulfur present in the first mixture is converted to H ₂ S of the second mixture, step c) the second mixture in the presence of an isomerization catalyst To obtain a third mixture, the third mixture containing a hybrid diesel fuel having a lower cloud point than the second mixture, _{2 S} is not removed prior to isomerization, comprising the step, and, d) obtaining a hybrid diesel fuel product away hybrid diesel fuel of the third mixture single, step.

In order to facilitate the production of such hybrid diesel fuel and / or to perform any or all of the methods described above, in some or other embodiments, the present invention provides hybrid diesel fuel production. directed to one or more systems for producing objects, mostly such a system, a) a mixing unit for forming a first mixture in combination with the vegetable oil diesel, vegetable oil first A unit comprising 10 weight percent or less of the mixture, b) a hydroprocessing unit for hydrotreating the first mixture to obtain a second mixture, wherein the triglyceride component of the first mixture is deoxygenated as an operable unit, and at least 95 atomic percent of the sulfur present in the first mixture is converted to H _{2 S} in the second mixture And c) an isomerization unit for isomerizing the second mixture in the presence of an isomerization catalyst to obtain a third mixture, wherein the third mixture has a lower cloud point than the second mixture A unit containing diesel fuel, in which the H ₂ S of the second mixture has not been removed prior to isomerization.

  What has been described above is a rather broad overview of the features of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of the invention.

  For a more complete understanding of the present invention and its advantages, the following description is now made in conjunction with the accompanying drawings.

FIG. 2 illustrates a method for producing a hybrid diesel biofuel composition in flow diagram format, in accordance with some embodiments of the present invention.

FIG. 2 schematically illustrates a system for performing the method as illustrated in FIG. 1 according to some embodiments of the invention.

1. Introduction Embodiments of the present invention are directed to methods (processes) and systems for co-processing vegetable oil and petroleum diesel to obtain a hybrid diesel (bio) fuel composition. In some such embodiments, the present invention is directed to a method (and system for carrying out such a method) of co-processing a mixture of vegetable oil and petroleum diesel in the following two stages, the two stages and Hydrotreating the mixture first to obtain a sulfur-reduced hybrid intermediate, followed by treating the hybrid intermediate with an isomerization unit to obtain a low cloud point hybrid diesel product that is partly biomass derived, That's it. Low cloud point hybrid diesel products usually have a cloud point within (or at least close to) that of standard diesel.

A unique aspect of at least some of the above embodiments of the present invention is that there is no intermediate stage removal of H ₂ S and NH ₃ between the hydroprocessing and isomerization steps. . In some such embodiments, this elimination of the intermediate stage removal of H ₂ S / NH ₃ was made possible by a nitrogen tolerant / resistive catalyst, which is a Miller US patent application. No. 12 / 181,652, incorporated herein by reference. With the elimination of such H ₂ S / NH ₃ intermediate stage removal, the efficiency of such large scale co-processing is greatly increased, thereby reducing overall production costs.

2. Definitions Certain terms and phrases are defined as they were originally used throughout this description, while certain other terms used in this description are defined below.

  As used herein, the prefix “bio” refers to association with renewable resources of biological origin, such resources generally excluding fossil fuels.

  As defined herein, a “biological oil” is an oil containing any triglyceride obtained at least in part from a biological source such as but not limited to cereals, plants, microalgae, and the like. Point to. Such oil may further comprise free fatty acids. The biological source is hereinafter referred to as “biomass”. For more on the advantages of using microalgae as a source of triglycerides, see R.C. Baum, “Microalgae are Possible Sources of Biodiesel Fuel,” Chem. & Eng. News, vol. 72 (14), pp. 28-29, 1994. As used herein, the terms “vegetable oil”, “cereal oil” and “biological oil” will generally be used interchangeably.

（式中、ｘ、ｙ、及びｚは、同一であっても異なっていてもよく、ｘ、ｙ、及びｚにより定義される１つ又は複数の分岐は不飽和領域を有することができる）。 As defined herein, “triglyceride” refers to a class of molecules having the following molecular structure:

(Wherein x, y, and z may be the same or different, and one or more branches defined by x, y, and z may have unsaturated regions).

（式中、「Ｒ」は、大抵は、飽和（アルキル）炭化水素鎖又はモノ若しくはポリ不飽和（アルケニル）炭化水素鎖である。）
を有するクラスの有機酸である。 As defined herein, a “carboxylic acid” or “fatty acid” has the general formula:

(Wherein “R” is usually a saturated (alkyl) hydrocarbon chain or a mono- or polyunsaturated (alkenyl) hydrocarbon chain.)
A class of organic acids having

  As defined herein, “lipids” refers broadly to a class of molecules including fatty acids and tri, di, and monoglycerides.

  “Hydrolysis” of triglycerides yields free fatty acids and glycerin, and such fatty acid species are also commonly referred to as carboxylic acids (see above).

  “Transesterification” or simply “esterification” refers to the reaction between a fatty acid and an alcohol to yield an ester species.

  “Hydroprocessing” or “hydrotreating” refers to a process or process in which a hydrocarbon-based material and hydrogen are reacted with a catalyst, typically under pressure (hydrogenation is non-hydroprocessing). Can be catalytic). Such processes include, but are not limited to, hydrodeoxygenation (of oxygenated species), hydrotreating, hydrocracking, hydroisomerization, and hydrodewaxing. For examples of such steps, see Cash et al. US Pat. No. 6,630,066; and Elomari US Pat. No. 6,841,063. Embodiments of the present invention utilize such a hydrogenation process to convert triglycerides to paraffin. The terms “hydroprocessing” and “hydrotreating” are used interchangeably herein.

  “Isomerizing” as defined herein typically refers to a catalytic process that converts an n-alkane to a branched isomer. ISODEWAXING (trademark of CHEVRON USA Inc.) catalyst is a typical catalyst used in such a process. See, for example, Zones et al. US Pat. No. 5,300,210; Miller US Pat. No. 5,158,665; and Miller US Pat. No. 4,859,312.

  “Transport fuel” as defined herein refers to a hydrocarbon-based fuel suitable for consumption by means of transport. Such fuels include but are not limited to diesel, gasoline, jet fuel and the like.

  “Diesel fuel” as defined herein is a material that is suitable for use in diesel engines and complies with at least one of the latest editions of the following standards: ASTM D975 “Standard for Diesel Fuel Oil”; European Standard CEN90; Japan Fuel Standard JIS K2204; The United States National Conference on Weights and Measurements (NCWM) 1997 Guidelines for High Quality Diesel Fuel; and The United States Engine Quality Standards .

  The term “biodiesel” as used herein refers to a diesel fuel that is at least significantly derived from biological feedstock and that is mostly compatible with ASTM International Standard Test Method D-6751. Often biodiesel is blended with general purpose petroleum diesel. B20 is a blend of 20 percent biodiesel and 80 percent general purpose diesel. B100 means pure biodiesel.

  As defined herein, “universal biodiesel” refers to ester-based biodiesel produced via transesterification of a triglyceride-containing vegetable oil.

  As used herein, the term “hybrid diesel biofuel” refers to co-processing (hydrotreating + isomerizing) vegetable oil and general purpose (petroleum) diesel according to the methods and systems of the invention. Specifically refers to the diesel produced.

  As defined herein, “pour point” refers to the lowest temperature at which a fluid flows or flows. See, for example, ASTM International Standard Test Methods D5950-96, D6872-03, and D97.

  As defined herein, “cloud point” refers to the temperature at which a fluid begins to phase separate due to crystal formation. See, for example, ASTM standard test methods D5773-95, D2500, D5551, and D5771.

As defined herein, "n" is an integer "C _n" describes a hydrocarbon or hydrocarbon-containing molecule or fragment (e.g., alkyl or alkenyl group), "n" is either linear It means the number of carbon atoms in a fragment or molecule, whether branched or not.

3. Methods As previously mentioned with reference to FIG. 1, in some embodiments, the present invention provides one or more of the methods for co-processing vegetable oil with general-purpose diesel to obtain a hybrid (bio) diesel fuel product. directed to methods, such methods are mostly, (step 101) forming a first mixture in combination with diesel vegetable oil, vegetable oil constitutes up to 10% by weight of the first mixture, (Step 102) hydrotreating the first mixture to obtain a second mixture, wherein the triglyceride component of the first mixture is deoxygenated and at least 95 atoms of sulfur present in the first mixture. % is converted to H _{2 S} in the second mixture, the step (step 103) third mixture was isomerized a second mixture in the presence of an isomerisation catalyst Obtaining a step, a third mixture containing a hybrid diesel fuel having a second lower mixture cloud point, H _{2 S} of the second mixture has not been removed prior to isomerization, step, and, (step 104) isolating a third mixture of hybrid diesel fuel to obtain a hybrid diesel fuel product.

In some embodiments of such a method as described above, the isomerization catalyst is sufficiently resistant to sulfur, making it unnecessary to remove H ₂ S (from the second mixture) prior to isomerization. In some such embodiments, the first mixture contains greater than 50 ppm nitrogen component. In some or other such embodiments, the first mixture contains greater than 50 ppm nitrogen component.

  In some such embodiments as described above, the isomerization step produces n-paraffins that produce advantageous fuel properties relative to the fuel properties of non-isomerized paraffin (ie, n-paraffin or n-alkane) products. Even though the product itself could gain use as a fuel or other commodity. One such fuel property that can be improved by isomerization is cloud point, that is, isomerization can lower the cloud point of the mixture.

Typically, isomerization is performed using an isomerization catalyst. Such isomerization catalysts are supported on SAPO-11, SM-3, SSZ-32, ZSM-23, ZSM-22, and similar such supports and / or beta or zeolite Y. molecular _{sieves, SiO 2, Al 2 O 3} , SiO 2 -Al 2 O 3, and on combinations thereof, Pt or Pd, include traditionally. Traditionally, isomerization is carried out at a temperature of about 500 ° F to about 750 ° F. The operating pressure is typically 200 to 2000 pounds force per square inch gauge (psig), more typically 200 psig to 1000 psig. The hydrogen flow rate is typically 50-5000 standard cubic feet / barrel (SCF / barrel). For other suitable isomerization catalysts, see, eg, Zones et al. US Pat. No. 5,300,210; Miller US Pat. No. 5,158,665; and Miller US Pat. No. 4,859,312. Please refer.

An important advantage of the present invention is that the intermediate removal of H ₂ S / NH ₃ between hydroprocessing and isomerization can be eliminated, which means that the isomerization catalyst is resistant to sulfur and nitrogen. Provided by. Accordingly, in some such embodiments described above, the isomerization catalyst contains an active metal catalyst (eg, Pt) on a support, which is a Miller US patent filed July 29, 2008. Such as any of the catalysts described in application Ser. No. 12 / 181,652, incorporated herein by reference. For the most part, the silicoaluminophosphate support described by Miller is designated as SM-7, which is a similar structure to the generic SAPO-11. Accordingly, in some of the above or other embodiments as described above, the isomerization catalyst contains Pt (and / or other active metals such as Pd) on the SAPO-11 support. The reaction conditions for such isomerization are typically within the parameters of traditional isomerization methods (see above).

  With respect to the catalytically propelled isomerization step described above, in some embodiments, the methods described herein may be used to convert an n-paraffinic product to a fixed stationary bed, fixed fluidized bed, or moving bed of catalyst. Can be carried out by contacting with. In one embodiment currently contemplated, trickle-bed operation is used, in which case the feedstock is drowned through a stationary fixed bed, usually in the presence of hydrogen. See Miller et al. US Pat. Nos. 6,204,426 and 6,723,889 for examples of the action of such catalysts.

  In some embodiments of such above methods, the vegetable oil originates from a biomass source selected from the group consisting of cereals, plants, microalgae, and combinations thereof. Thus, the term “vegetable oil” is indeed very broad and can be extended to encompass generally oils of biological origin (see definition above). One skilled in the art will recognize that any biological source of lipids can generally serve as biomass from which biologically derived oils (eg, vegetable oils) containing triglycerides can be obtained. Some such sources can be more economical and more acceptable for local cultivation, and sources that do not have food can be more attractive (not seen to compete with food) It will be further recognized. Exemplary vegetable oil / oil feedstocks include but are not limited to canola, soybean, rapeseed, palm, peanut, jatropha, yellow fat, algae, and the like.

  In some embodiments of such a method as described above, the hydrotreating step includes a hydroprocessing / hydrotreating catalyst and a hydrogen-containing environment. For a general review of hydroprocessing / hydrotreating, see, for example, Rana et al., “A Review of Revenue Advanced Technologies on Process Technologies,” a review of recent advances in process technology for heavy oil and residual oil upgrades. Heavy Oils and Residua), Fuel, vol. 86, pp. 1216-1231, 2007. See Craig et al. US Pat. No. 4,992,605 for an example of how triglycerides can be hydrotreated to produce paraffinic products.

In some embodiments of such a method as described above, the hydrotreating step includes a hydrotreating catalyst containing an active metal or metal alloy hydrotreating catalyst that is operatively integrated with the refractory support material. , Otherwise use. In some such embodiments, the active metal catalyst component is selected from the group consisting of a cobalt-molybdenum (Co-Mo) catalyst, a nickel-molybdenum (Ni-Mo) catalyst, a noble metal catalyst, and combinations thereof. . In these or other embodiments, the refractory support material is typically a refractory oxide support—which includes, but is not limited to, Al ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , combinations thereof, and the like. -Not included. In some specific embodiments, the hydrotreating step comprises the use of an alumina supported nickel-molybdenum catalyst.

In some embodiments of such a method as described above, the hydrotreatment is performed at a temperature of 550 ° F to 800 ° F. In some such embodiments, the hydrotreatment is performed under a H ₂ partial pressure of 400 psig to 2000 psig. In some or other such embodiments, the hydrotreatment is performed under a H ₂ partial pressure of 500 psig to 1500 psig.

As a hydrotreatment that efficiently removes sulfur (in the form of H ₂ S), in some embodiments, the second mixture is other than H ₂ S and typically has a reduced sulfur component of 20 ppm or less, Preferably it has 10 ppm or less. Note that the hydrotreatment also allows for the removal of oxygen (in the form of H ₂ O).

  Hydroprocessing can also affect the cloud point, typically lowering the cloud point of the second mixture than the first mixture. In some such embodiments, the second mixture has a cloud point of −6 ° C. or lower, and in some or other embodiments, the second mixture has a cloud point of −8 ° C. or lower. Have.

Isolation of the hybrid diesel (bio) fuel from the third mixture is accomplished by simply removing the H ₂ S present, and this stage of H ₂ S removal is typically a hydroprocessing and isomerization step. Easier than its removal in between. In some embodiments, the isolation of the hybrid diesel fuel is at least partially achieved by stripping the third mixture H ₂ S.

Typically, the method embodiments of the present invention produce a hybrid diesel (bio) fuel with low sulfur content. In some embodiments, the hybrid diesel fuel has a sulfur component other than H ₂ S of 20 ppm or less, and in some such embodiments, 10 ppm or less.

  Isomerization of the second mixture can reduce its pour point to obtain a hybrid diesel biofuel with a lower pour point than the second mixture, as described in the method embodiments above. In some such embodiments, the hybrid diesel fuel has a cloud point of −10 ° C. or less.

4). System As already mentioned in the previous section and with reference to FIG. 2, in some embodiments, the present invention provides for co-processing vegetable oil with petroleum diesel to provide the hybrid diesel fuel product, and And / or directed to one or more systems 200 for performing any or all of the above methods. Thus, still referring to FIG. 2, in some or other such embodiments, the present invention is generally directed to one or more systems for producing hybrid diesel products, such systems usually the following units - a mixing unit 201 for forming the first mixture in combination with diesel vegetable oil, vegetable oil constitutes up to 10% by weight of the first mixture, units, the first mixture A hydroprocessing unit 202 for hydrotreating to obtain a second mixture, the unit being operable to deoxygenate the triglyceride component of the first mixture and present in the first mixture at least 95 atomic percent of the sulfur is converted to H _{2 S} in the second mixture, isomers unit, as well as a second mixture in the presence of an isomerisation catalyst A isomerization unit 203 to obtain a third mixture, and a third mixture containing a hybrid diesel fuel having a second lower mixture cloud point, H _{2 S} in the second mixture prior to isomerization A unit that has not been removed is provided.

In some embodiments of such systems as described above, the system 200 further comprises an isolation unit 204 for isolating the third mixture hybrid diesel fuel to obtain a hybrid diesel fuel product. In some or other such embodiments, the isolation unit comprises an H ₂ S stripping unit.

  Preferred isomerization units utilize an ISODEWAXING ™ catalyst and preferably contain SM-7 or SSZ-32. In some or other such embodiments, the isomerization catalyst contains Pt on the SM-7 support.

  Mostly, all the above system units are configured to process vegetable oils according to the method described in the third section. Further, although there are typically adjacent relationships between the various units including the system 200, this need not always be the case. Such relationships may be affected by existing infrastructure and / or other economic considerations.

5. Variations In some variously contemplated alternative embodiments, the intermediate (second) mixture is catalytically isomerized to an isomerized intermediate mixture prior to separation into the various components. Thus, the method / system parameters can be set to produce a hybrid (bio) fuel that is not diesel. Such variations result in additional method and corresponding system embodiments having different steps and arrangements, otherwise mostly as described for the above embodiments.

  As stated and / or implied, other plant or cereal oils and / or algae-derived oils may also be used, at least in part, in the methods / systems of the invention in a manner similar to vegetable oils. Those skilled in the art will recognize that, and even animal fats (eg, beef tallow) may be used. In addition, in determining the composition of the starting mixture, economics, renewables, and fuel properties (eg cloud point) can interact delicately, resulting in a final product.

6). Examples The following examples are provided to demonstrate specific embodiments of the invention. It should be appreciated by those skilled in the art that the methods / systems disclosed in the following examples merely present exemplary embodiments of the present invention. However, in view of the present disclosure, those skilled in the art will appreciate that many changes may be made to the particular embodiments described and still obtain similar or similar results without departing from the spirit and scope of the invention. Should be recognized.

Example This example serves to illustrate an exemplary system for performing a method embodiment of the present invention to produce a hybrid diesel biofuel in accordance with some embodiments of the present invention.

Using a isomerization catalyst of Pt catalyst on SM-7, a 95/5 diesel / canola oil mixture having approximately 500 ppm of sulfur (S) was hydrotreated in a hydrotreating unit and hybrid diesel intermediate Got the body. Note that diesel treated with hydroprocessing and without canola oil has a significantly reduced sulfur content (less than 6 ppm), but has a relatively high cloud point (ie, -7 ° C, see Table 1 below). I want to be. This hybrid diesel intermediate mixture with added canola oil was treated with an isomerization unit using ISODEWAXING ™ (IDW) catalyst (Pt on SM-7) to produce a relatively low cloud point (−13 A hybrid diesel product having a C) was obtained. This lower cloud point allows diesel to be used in colder climates. In the entire effluent from the first (hydrotreating) stage to the second (isomerization) stage, intermediate stage removal of H ₂ S and NH ₃ was not necessary.

Table 1 below compares the yield / characteristics of the products resulting from diesel and diesel / canola oil feeds processed according to some embodiments of the present invention. HDS treatment conditions are as follows -0.7LHSV, total pressure 700 psig, _{H 2} pressure is 525 psig, and _{H 2} were 1200SCFB-.

  Due to the high activity of the isomerization catalyst, it is possible to operate at 684 ° F. which is not much higher than the 650 ° F. of the hydrotreating catalyst. This will extend the operational life of the system. It also allows the use of an isomerization catalyst downstream of the hydrotreating catalyst in the same reactor (although another reactor is preferred).

7). Conclusion What has been described above is an explanation of a method and system for co-processing vegetable oil and petroleum diesel to obtain a hybrid diesel biofuel composition. As previously mentioned, in some embodiments, the present invention is directed to a method / system for co-processing a mixture of vegetable oil and petroleum diesel in the following two stages, the first being Hydrotreating to obtain a sulfur-reduced hybrid intermediate, followed by treating the hybrid intermediate with an isomerization unit to obtain a low cloud point hybrid diesel product that is partially derived from biomass. At least the notable benefit of such a method / system is that no intermediate stage removal of H ₂ S and NH ₃ is required between the hydroprocessing and isomerization stages.

  All patents and publications cited herein are hereby incorporated by reference to the extent not inconsistent with this specification. Certain configurations, functions, and operations of the above embodiments are not necessary to practice the invention, but are merely included in the description for completeness of the exemplary embodiment or embodiments. Will be understood. In addition, the specific configurations, functions, and operations described in the above cited patents and publications may be practiced in conjunction with the present invention, but they are not essential to the practice of the invention. It will be understood. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without actually departing from the spirit and scope of the invention as defined by the appended claims. Should.

Claims (23)

a) combining vegetable oil with diesel to form a first mixture, wherein the vegetable oil comprises 10 weight percent or less of the first mixture;
b) hydrotreating the first mixture in a first stage to obtain a second mixture, wherein the triglyceride component of the first mixture is deoxygenated and at least 95 atoms of sulfur present in the first mixture; The percentage is converted to H ₂ S of the second mixture, step;
c) a second mixture in the presence of an isomerisation catalyst in a second stage comprising the steps of: obtaining a third mixture was isomerized, the third mixture has a low Ku and -10 ° C. or less cloud point than the second mixture Containing a hybrid diesel fuel, wherein H ₂ S and NH ₃ of the second mixture have not been removed prior to isomerization of the second mixture in the second stage, and
d) isolating a third mixture of hybrid diesel fuel to obtain a hybrid diesel fuel product,
A method comprising:
The isomerization catalyst contains Pt on a SM-7 support or a SAPO-11 support;
Way .   The method of claim 1, wherein the first mixture contains greater than 50 ppm nitrogen component. The method of claim 1 wherein the first mixture contains up to 500 ppm of nitrogen component.   The process of claim 1, wherein the isomerization catalyst contains Pt on a SM-7 support.   The process of claim 1 wherein the isomerization catalyst contains Pt on a SAPO-11 support.   The vegetable oil contains one or more bio-derived oils selected from the group consisting of canola, soybean, rapeseed, palm, peanut, jatropha, yellow fat, algae, and combinations thereof. the method of.   Metal or metal alloy active hydrotreating catalyst wherein the hydrotreating step is selected from the group consisting of a cobalt-molybdenum (Co-Mo) catalyst, a nickel-molybdenum (Ni-Mo) catalyst, a noble metal catalyst, and combinations thereof The method of claim 1, comprising a hydroprocessing catalyst containing components.   The method of claim 7, wherein the hydrotreating catalyst comprises a refractory oxide support. Containing support component hydrotreating catalyst is selected from the group consisting of _Al 2 _{O 3} and _SiO 2 _-Al 2 _{O 3,} The method of claim 7.   The method of claim 1, wherein the hydrotreating utilizes an alumina supported nickel-molybdenum catalyst. The method of claim 1, wherein the hydrotreatment is performed at a temperature of 550 ° F. to 800 ° F. (288 ° C. to 427 ° C.) . The method of claim 1, wherein the hydrotreatment is performed under a H ₂ partial pressure of 400 psig to 2000 psig (2.76 MPa (gauge pressure) to 13.8 MPa (gauge pressure)) . The method according to claim 1, wherein the hydrotreatment is carried out under a H ₂ partial pressure of 500 psig to 1500 psig (3.45 MPa (gauge pressure) to 10.3 MPa (gauge pressure)) . The method according to claim 1, wherein the second mixture has a sulfur component of 20 ppm or less other than H ₂ S. Second mixture - with a 8 ° C. below the cloud point, the method according to claim 1. The method according to claim 1, wherein the hybrid diesel fuel has a sulfur component of 10 ppm or less other than H ₂ S. The process of claim 1, wherein the isolation of the hybrid diesel fuel is at least partially achieved by stripping H ₂ S of the third mixture. A system for producing a hybrid diesel fuel product,
a) a mixing unit for combining vegetable oil with diesel to form a first mixture, wherein the vegetable oil comprises 10 weight percent or less of the first mixture;
b) a hydroprocessing unit for hydrotreating the first mixture to obtain a second mixture, the unit operable to deoxygenate the triglyceride component of the first mixture, and A unit wherein at least 95 atomic percent of the sulfur present in one mixture is converted to H ₂ S in the second mixture; and
The second mixture in the presence of c) isomerization catalyst be a isomerization unit to obtain a third mixture was isomerized, the third mixture has a low Ku and -10 ° C. or less cloud point than the second mixture A unit containing hybrid diesel fuel, wherein H ₂ S and NH _{3 of} the second mixture have not been removed prior to isomerization,
A system comprising:
The isomerization catalyst contains Pt on a SM-7 support or a SAPO-11 support;
System . 19. The system of claim 18 , further comprising an isolation unit for d) isolating the third mixture of hybrid diesel fuel to obtain a hybrid diesel fuel product. 20. The system of claim 19 , wherein the isolated catalyst contains Pt on a SM-7 support. The system of claim 19 , wherein the isolation unit comprises an H ₂ S stripping unit.   The method of claim 1, wherein all effluent from the first stage goes to the second stage. All effluent from the first stage hydrotreating unit and isomerization unit to face the second stage is consists system of claim 19.

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