JP2020143299A - Fuel and compounding combination thereof - Google Patents

Abstract

To provide the fuel and compounding combination that is useful as the fuel, wherein the fuel is manufactured using a light tight oil and a high sulfur fuel oil, has very low sulfur and nitrogen, and is substantially metal free.SOLUTION: The fuel is obtained by combining the light tight oil with a hydrogen-conversion reaction effluent having lighter materials derived from a treated soluble deasphalting oil and a high sulfur fuel oil, or with other residues treated by residues hydrogenation. An unconverted oil passes through solvent separation to remove insoluble residual metals and asphaltene, then, a soluble deasphalting oil is formed, followed by hydrogen-treatment or hydrogen-conversion to form said treated soluble deasphalting oil. Sulfur content of the fuel obtained in combination is 0.5 wt.% or less.SELECTED DRAWING: Figure 1

Description

The present invention provides a novel method for producing a fuel and a novel method for preparing a composition assuming a fuel having a wide range (C3 or C5 to C20 or more) of hydrocarbons produced from crude oil. Preferred feedstocks in the methods of the invention are in conventional refineries such as refinery intermediate residues, high sulfur fuel oils, low sulfur fuel oils or light tight oils, condensates, superheavy oils, tarsands and asphalt. Is a hydrocarbon source that has been considered unfavorable as a raw material oil. The fuel provided by the present invention is an ultra-clean fuel having a very low amount of sulfur and nitrogen and a very low amount of metal as measured by many techniques, with almost no metal detected and substantially containing metal. It is a particularly cost-effective fuel not only for use on large marine transport vessels, but also on land for large onshore combustion gas turbines, boilers and transport vehicles and trains.

The present invention presents at least three problems: (1) converting low-value hydrocarbons to high-value fuels, (2) cost-effectively reducing sulfur and nitrogen and substantially removing metals from the fuels. And (3) to adapt the fuel for use in combustion heaters such as offshore or land engines, combustion gas turbines, or boilers.

Certain hydrocarbon sources are undesirable as raw materials for refineries and may be undervalued by refineries. Traditional refineries seek to divide each barrel of crude oil with all or a wide range of hydrocarbons into feedstock from multiple fuel and downstream chemical products. Refineries often prefer feedstocks with a wide range of hydrocarbons. In competition where margins are often very small, a particular refinery not only meets customer supply constraints, but also balances the materials and energy required to meet all unit operations. Although most of the total carbon range of crude oil is required to achieve this, these refineries also tend to opt for feedstocks that do not cause processing problems or increase operating costs.

Traditional refineries have operational problems with very heavy crude oils such as Maya (Mexico), BCF-17 (Venezuela), and Oriente (Ecuador), which cause problems with equipment, operating and investment costs. encounter. Such problems can also occur with the treatment of oil shale obtained from organic-rich sedimentary kerogen-containing rocks and condensates.

Traditional refineries also face the problem of processing light tight oil, which is sometimes described as "missing most of the bottom of the barrel" compared to crude oil. Light tight oils (also simply referred to as tight oils) are now widely available as those produced from shale and other low permeability formations such as sandstone and carbonates. Compared to traditional crude oils, tight oils have an excess of light ends, but are referred to in refineries as the "vacuum gas oil" range or the "heavy residue" or "pressure residue" range, from 425 ° C or 565 ° C, respectively. It boils at high temperatures or has little or no hydrocarbons in the "bottom of the barrel" heavy range material. See Non-Patent Document 1.

As used herein, the terms "tight oil," "light tight oil," or "LTO" are (i) almost immeasurable or zero (0) sulfur in the range of% to 0.2% by weight. Oil Iguchi condensate with wide variation in source based on content, (ii) density, API (degrees) in the range 38-57 degrees, (iii) metal traces and (iv) hydrocarbon range, unaccompanied natural Means gas condensate or shale gas condensate, but not all are the same. LTOs from different sources have different distillation withdrawal fraction ranges. According to the description used for the range of fractions characterized by a particular refinery, exemplary variations in LTO are (a) 5 to 20% by weight liquefied petroleum gas range, (b) 10 to 35% by weight. Naphtha, (c) 15-30% by weight kerosene / jet range, (d) 15-25% by weight diesel and heavy fractions, (e) trace levels of 10% or more reduced gas oil, and (f) It may have a heavy residue of zero (0%) to about 5% by weight or more.

Such light tight oils, especially those with small amounts of heavy light oil and substantially zero or very small amounts of heavy residue, are substantially free of heavy hydrocarbons in the bottom fraction in the light oil. Sulfur and metals in such gas oil, which do not contain a range of residues to provide a processing balance for hydrodesulfurization or other hydrocarbonization or corresponding residues sufficient to maintain process hydrogenation. Allows for cost-effective hydrotreating to reduce and decontaminate, or has sufficient lubricity for use in certain types of engines. See, for example, Non-Patent Document 2 which provides a range of components for a particular tight oil. Mixing tight oil with heavy asphalt crude oil is a desirable distillation profile for many refineries in order to balance the mixture of product extracts from the crude oil distillation column and adapt it to the operation of many refineries. It is meaningful because it brings about. This is recognized by those skilled in the art, but if it is carried out, it will lead to compatibility problems such as asphaltene instability (Non-Patent Document 3).

Also in high sulfur fuel oil or "HSFO", which may be described as part of the "bottom of the barrel" or "missing most of the top of the barrel" compared to crude oil. Traditional refineries face processing problems. In other applications in the art, the terms "high sulfur fuel oil" or "HSFO" have been assigned different, sometimes dissimilar, contradictory and confusing meanings in various technical articles, patents and legislation. Some of them change over time. The widely used term "high sulfur fuel oil" is a light, low boiling point but high sulfur (and therefore high smoke) kerosene containing more than 3.5% by weight of sulfur, including those other than those used in fuels. Used to describe a wide range of materials, including heavy marine bunker fuels or masts with quantities or other heavy residues, including "barrel bottom" material, and in some cases clear or uniform. Does not have specifications applicable to. Certain indicator reporting systems use HSFO as a fuel oil with a sulfur content of RMG 3.5%, based on the ISO8217 specification, while others use different sulfur contents.

As used herein and in the claims, "high sulfur fuel oil" or "HSFO" is a fuel having a sulfur content greater than 0.50% m / m (0.5% by weight). Means the substance used as. The terms "heavy oil," "heavy residual oil," "residue," "residue," or "other heavy oil," "tar sands," and "ultra-heavy oil" as used herein are sulfur. Contains petroleum-derived hydrocarbon-based substances having a content of more than 0.50% m / m (0.5% by weight). The term "high sulfur" means the lower of the fuel's target sulfur content limit or above the applicable statutory sulfur limit.

Another problem is that the market for high sulfur fuel oils is shrinking and large amounts of HSFO cannot be blended or transported. Many countries that burn HSFO to meet electricity demand are substituting natural gas for local supply. For example, in 2015 Mexico became an HSFO exporter from a net importer when power plants switched to a local supply of natural gas.

For example, in some states of the United States, the requirement for petroleum for home heating has been changed to less than 500 ppm sulfur instead of 2,000 ppm or more sulfur. As a result, certain pipelines and distribution networks have high fuel oils in certain areas, especially in areas where local refineries do not have the feedstock, equipment or technology to efficiently process low fuel oils. Refining to transport "high fuel oil" in connection with the impact of oversupply. For many refinery managers, the practical choice of improving the quality of the residue to better address the required investment with HSFO return on investment is much lower than alternative investment. The use of HSFO as a turbine fuel causes corrosion and contamination problems and is unreliable.

In prior art refinery designs using atmospheric crude oil and / or vacuum distillation units, solvent separation, hydrothermalization, gasification and many other unit operations, each barrel of crude oil feedstock has a different application or downstream treatment. Divide into multiple products with different specifications for each.

Hydrogenation skimming refineries convert crude oil into multiple products similar to topping refineries, but typically put a weight on reformers that also produce the hydrogen consumed by the hydrogenation process in diesel production. Addition of quality naphtha is restricted. Hydrogenated skimmers, such as topping refineries, typically produce a wide range of gasoline, kerosene, diesel and fuel oils for local consumption, rather than just one product. Various embodiments are known in the art to adapt hydrogenation, including separate series or parallel hydrogenation reactor zones or integrated hydrogenation reactor zones. Patent Document 1 of Cash et al. And the references cited therein disclose integrated hydrocracking and hydrotreating of different feedstocks, containing hydrogen and liquids from separate hydrotreating zones. The inclusion streams are distributed or combined by the disclosed methods.

Early boiling systems are described in Johannson's Patent Documents 2 (1961) and 3 (1965), and the hydroconversion of heavy oils and residues with a boiling bed reactor is in the art. It is known. The boiling bed reactor has fluid contact between the heavy hydrocarbon solution and hydrogen in the presence of a catalyst in the reaction vessel, with various associated auxiliary gas-liquid separators and hydrogen composition and regeneration flow, and sulfur content. Gas treatment systems are well known and are commercially practiced in the art. Patent Document 4 of Collier et al. Describes a series of boiling reactors, and Patent Document 5 describes a hydrogenation conversion step by a boiling reactor and a hydrogenation treatment step by a fixed bed hydrogenator. Patent Document 6 (2014) by Baldassari et al. Describes various hydroconversions, including various integrated hydroconversion, hydrocracking and hydrotreating apparatus, along with hydroconversion, hydrocracking and hydrotreating steps. Hydrogenation decomposition and hydrogenation treatment catalysts are also described. Baldassari et al. Further summarize the various catalytic compositions and condition ranges for distillation and heavy oil hydrogenation treatments and classify the conditions for hydrocracking and residue hydroconversion. All of these are known to those of skill in the art in the art of hydrogenation.

Various aspects of the use of solvent separation to extract the deasphalized oil from the pitch in the heavy residue stream and use the deasphaltated oil as a raw material for the hydrogenation process are to produce multiple product streams. Known in the art as used. For example, Patent Document 7 (2010) of Brierley et al. Separates the feedstock based on its solubility in liquid solvents such as propane or other paraffinic solvents such as butane and pentane, and de-asphalates without cracking or decomposition. Describes solvent deasphaltization for the production of oils. The pitch residue contains a high content of metal and sulfur. According to Brierley et al., Deasphaltated oils are used to remove sulfur, nitrogen and metals, as described in the references for the production of several products, including naphtha, kerosene, diesel and residues. It is hydrolyzed and hydrotreated.

Patent Document 8 (2009) by Lenglet describes a method for pre-producing crude oil for producing two non- asphaltene oils and pre-distillation, vacuum distillation, solvent deasphaltation, hydrogenation treatment, hydrocracking and residues of asphaltene oils. It describes the preparation of multiple products with hydroconversion. Non-Patent Document 4 describes unit design, catalyst selection, hydrogen consumption and other operations for producing products in which sulfur is removed by hydrogenation and sulfur is reduced to less than 8 ppm by using a highly active Ni / Mo catalyst. The conditions are described. Page 6 of Non-Patent Document 5, Advanced Purification Technology, Publication No. 113/2013 of Specified Edition of Catalagram also uses a highly active CoMo catalyst to remove sterically hindered sulfur, and a highly active NiMo catalyst to retain sterically hindered sulfur. The hydrogenation treatment to remove the above to 10 ppm is described.

Thus, traditional refineries have made many improvements to address the technical problems that arise from treating light tight oils and residues, but without a solution, serious problems remain. ing. Such problems create technical ditches and result in substantially inadequate use of light tight oils and high sulfur fuel oils.

PCT / US1999 / 00748 U.S. Pat. No. 2,987,465 U.S. Pat. No. 3,197,288 U.S. Pat. No. 6,270,654 U.S. Pat. No. 6,447,671 U.S. Patent Publication No. 201402217113 (U.S. Patent Application No. 13 / 758,429) U.S. Pat. No. 7,686,941 International Application PCT / FR2006 / 000671 (US Patent Application 11 / 912,771)

"Refining America's New Light Tight Oil Production", OPIS 16th Annual National Suppley Summit, Las Vegas October 2014) Baker & O'Bri "The North Dakota Petroleum Council Study on Bakeri Products Bakken Crude characterization Task Force" (2014), Turner & Mason Benoit et al., "Overcoming the Challenges of weight / shale oil refining", Processing Shale Feedstocks, (2014). Ackerson et al., "Revamping Diesel Hydrotrators For Ultra-Low Sulfur Using IsoTherming Technology" Shiflet et al., "Optimizing Hydrodesulfurization Catalysis Systems for Hydrocracking and Diesel Hydrotreating Applications, Flexibility Technology Catalysis Technology Technology", Hydrodesulfurization Catalysis 113/2013, page 6

The present invention makes it possible to use light tight oils and high sulfur fuel oils to produce large quantities of fuels with very low sulfur and nitrogen and virtually metal free, effectively and at low cost. And fill the technical gap. The fuel is particularly useful for marine applications as well as large-scale land applications such as combustion gas turbines for power generation. The terms "essentially / substantially metal-free" or "zero metal" as used herein and in the claims range from zero (zero) to less than 100 ppb (billion percent). It means a metal content or a content that is so low that it is difficult to reliably measure it with conventional online instruments.

The present invention provides a novel method for preparing a composition having a wide range (C3 or C5 to C20 or more) of hydrocarbons and assuming a fuel produced from crude oil from high sulfur fuel oil and light tight oil. A preferred feedstock for the method of the invention is a hydrocarbon feedstock, such as high sulfur fuel oil or light tight oil, which has been previously unfavorable as a feedstock in conventional refineries.

The fuel of the present invention is an ultra-clean fuel that is very low in sulfur and nitrogen and is substantially free of metals, especially for use on large offshore transport vessels, as well as on large onshore combustion gas turbines, boilers and transport. It is a particularly cost-effective fuel on land for vehicles and trains.

In conventional refining, crude oil feedstock is extracted into many parts, each part being sent to a separate market channel downstream. In contrast, we take "barrel top" light tight oil and "barrel bottom" high sulfur fuel oil and combine them at low cost to produce fuels that are made from crude oil and have a wide range of hydrocarbons. Assuming, we found that we could produce fuel.

The present invention provides a low cost system that combines light tight oil and residual oil at low cost to produce a large amount of clean fuel on a commercial scale. The fuel replaces high sulfur bunker fuels and other heavy residues used in commercial transport ships and power plant combustion systems. The present invention provides such fuels and methods and devices for producing such fuels to reduce sulfur, nitrogen and harmful metal emissions in a cost-effective manner. For the shipping industry, the novel configurations of the present invention provide the amount of low-cost, low-sulfur marine fuel required to meet or exceed global marine sulfur reduction targets.

In addition, the fuels of the present invention are also crude oil or heavy in large onshore combustion turbines deployed in single-cycle or combined-cycle power plants, such as those that produce electricity and desalinated water, for example. An alternative to burning the residue is provided. The turbine that burns the fuel of the present invention emits significantly less turbine exhaust gas from NOx, SOx, CO _2, soot, harmful metals and other combustion by-products, and is contaminated heavy oil depending on the source. Or when burning refined residual oil, there is less contamination in high temperature zones or under ash formation conditions.

These new processes use empirical steps to reduce manufacturing costs while controlling the sulfur content of the final product below target sulfur levels in a surprisingly effective way. In conventional purification, the extracts are separated and then recombined.

For example, in the prior art of compounding, the focus of compounding is to form a gasoline, diesel, or jet fuel, and all of the separate refinery products are compounded to form a single fuel. is not. That is, crude oil is not separated into a large number of fractions by distillation, but all are then recombined. For example, the technique avoids blending large amounts of diesel range material into the gasoline range. Also, the end user does not have to mix diesel with gasoline. Similarly, the confusion associated with the terms "kerosene" and "light fraction" is the distillation column fraction boundary point or other at normal pressure over a temperature range (eg 190 ° C to 250 ° C or 180 ° C to 230 ° C). It is not uniformly defined based solely on established standards, often due to the use of these terms with different meanings between the same, overlapping, or different reference materials. For example, the EIA defines "intermediate distillates: refined petroleum products containing the general classification of distilled fuel oils and kerosene". Therefore, the purification boundary point in the temperature range is determined by the specifications of each product from the conventional refinery, is often set for each region, and is not defined based on the sulfur content. We have found that this is not optimal.

The term "component" as used herein is used in contrast to the unexpected phenomenon found by "combining components" in the practice of the present invention, as opposed to simply blending the components. To. The typical use of the term "ingredient" when referring to a combination of those by human intervention gives hope for the consequences of the presence of the ingredient. That is, the ingredients, when added, give the expected physical or chemical properties that are characteristic as a whole.

Conventional refineries do not mix gasoline with diesel or treated residual oil to produce fuel. Instead, separate the removals for different engine types.

What was not known to those skilled in the art of the essential oil technology until now disclosed by the present invention is a novel fuel formulation, with many light (L), intermediate (M) and heavy (H) configurations. It is the best way to select and / or obtain from the elements (taught and defined below) and to combine the selected components to form a low sulfur, substantially metal-free fuel. Such ones are looking at a warehouse filled with cooking ingredients, but there is no recipe for the lowest cost and lowest calorie cake, and the amazing interactions that occur by processing and combining ingredients in a particular way. It's very similar to a bakery who doesn't even know about the phenomenon.

Schematic diagram showing a basic apparatus and processing process that combines untreated light tight oil and treated high sulfur fuel oil to form a fuel with very low sulfur. Explanatory drawing showing that the processing of light cycle oil and high sulfur fuel oil is simplified to produce low sulfur fuel with adjusted flash point. Schematic diagram showing equipment layout and processing steps using crude oil alone or with light tight oil and high sulfur fuel oil to produce ultra-clean fuels with very low sulfur, nitrogen and metals. Teaching recipes for combinations of one or more components with new fuels and light (L), intermediate (M) and / or heavy (H) materials for forming such fuels, according to the invention. Explanatory drawing schematically showing the volume fraction and density profile of the reference fuel produced by the method, and the ranges of (L), (M) and (H) thereof. Teach recipes for combinations of one or more components with new fuels and light (L), intermediate (M) and / or heavy (H) materials to form such fuels (naturally). The volume fraction and density profile of the reference light condensate, which has the majority of the (L) present and can be used as the "upper barrel" (the naturally occurring (M) and (H) are small), is shown. Explanatory drawing which constitutes the fuel of this invention in combination with (H) from other sources such as "barrel bottom" (H) components of the barrel upper part.

The present invention provides a method of converting various hydrocarbon-based feedstocks from sources other than conventional crude oil, alone or with conventional feedstocks, to form fuels with a wide range of hydrocarbons. In the modified example, the fuel formed by the light tight oil supply raw material and the high sulfur fuel oil supply raw material is a hydrocarbon-converted liquid derived from the high sulfur fuel oil from the lowest boiling point of the light tight oil forming the fuel. It has a wide range of hydrocarbons up to the maximum boiling point of and forms the fuel.

In one embodiment, one or more high sulfur fuel oils are fed to the residue hydrogenation conversion zone and contacted with hydrogen in the presence of a catalyst in a boiling bed reactor under residual hydrogenation conversion conditions (1). ) A hydrogenation conversion product solution, a hydrogenation conversion reactor effluent separated into a purge gas containing hydrogen and sulfur, and (2) unconverted oil heading for solvent separation. Such unconverted oils are used as (A) feedstocks for soluble de-asphalated oils and (B) pitch treatments recovered in hydrogenation conversion reactors, along with separate or added high sulfur fuel oil feedstocks. Form the insoluble pitch to be sent. The product fuel is formed by combining all or part of the light tight oil with the hydrogenation conversion product liquid. In one variant, light tight oil is fractionated to remove overhead distillation gas, leaving the bottom of the separator combined with the hydroconversion zone product solution to form the fuel before use as part of the combination. .. In another variant, some of the feedstock for solvent separation has a high sulfur total oil that is added directly to the solvent separation or is supplied to the solvent separation in combination with the hydrogenation conversion reactor unconverted oil. .. Further, the additional high-sulfur fuel oil can be combined with the above-mentioned soluble deasphalized oil and supplied as a part of the raw material to be supplied to the hydrogenation conversion reactor. Fractionalizing light tight oil before adding it to the fuel combination, removing overhead distillation gas, and upper zone light distillers with hydrocarbons in the naphtha range and high boiling bottom distillates, taking into account the flash point and others. Minutes can be formed. In one variant, at least some of such light fractions are naphtha-rich and sent to a reformer or other air freshener unit operation to contact hydrogen under reforming conditions for a light treatment stream. To form. In another modification, all or part of the light treatment stream, the untreated light stream and the high boiling bottom fraction are combined with the hydrogenation conversion solution to form a fuel. In yet another variant, the effluent from the hydrogenation conversion reactor is fractionated and separated into two or more treated liquid fractions, at least the fraction having a sulfur content higher than the target sulfur content. One is used as part of the feedstock for the residue hydrogenation conversion reactor or as part of the feedstock for fractional distillation.

In one embodiment, the residue hydrogenation conversion zone integrates the residue hydrogenation conversion reactor with a heavy oil range hydrogenation treatment device and a distillation range hydrogenation treatment device, and a gas-liquid separator, hydrogen stream, purge gas, sulfur. Integrate one or more of the recovery steps and common treatment liquid recovery. In another variant, in such an integration, the treatment liquid recovery could be configured separately, allowing the measurement of the sulfur content of each stream and the adjustment of the flow rate to the combination zone, respectively, in practice. Form a fuel whose sulfur content is less than or equal to the target sulfur content. In the modified example, the treated product flow from the upper zone of the hydrogenation conversion reactor zone effluent is fractionated and separated into two or more hydrogenation conversion liquid distillates, and the sulfur content is higher than the above target sulfur content. At least one of the distillates having hydrogen is sent to another hydrogenation treatment zone and brought into contact with hydrogen under hydrogenation treatment conditions in the presence of a catalyst to carry out low-sulfur hydrogenation treatment having a sulfur content less than the above target sulfur content. Form a flow. Next, the hydrogenation treatment flow is combined with another hydrogenation conversion liquid fraction and the untreated flow derived from the light tight oil to form a fuel having an actual sulfur content equal to or less than the target sulfur content.

In one embodiment, the light tight oil feedstock has an API density in the range of 45-55 degrees, the high sulfur fuel oil has an API density in the range of 14-21 degrees, and the hydrogenation conversion solution has 26 degrees. With an API density in the range of ~ 30 degrees, the combination fuel product has an API density in the range of 37 to 43 degrees and a hydrogen content of less than 0.5% by weight. The actual sulfur content of the fuel of the present invention is adjusted to meet the target sulfur content within the IMO specifications for marine fuels or the turbine manufacturer's specifications for combustion gas turbines, as disclosed herein. can do.

Another embodiment of the present invention provides a method for co-treating crude oil with light tight oil and high sulfur fuel oil. Within the scope of the present specification and claims, the present inventors have defined the mass% or volume% of crude oil as the x-axis and the sulfur content as the y-axis in relation to the analysis or other measurement method of crude oil. Plot and define the "breaking point" as the point where the rate of increase per unit operation is high, the sulfur content begins to increase rapidly or exponentially from a horizontal or near position. The difference in operation is the change in unit volume of the distillate, the difference in increase is the change in sulfur content, and the slope is the amount of increase in operation. The slope with respect to the amount of increase in such operations moves sharply above 0.2 from zero or near-horizontal values, and rapidly exceeds 1 towards an exponential increase in sulfur content. Movements and break points vary based on crude oil or other feedstock to the distillation column. Thus, "break point retrieval" or "sulfur break point retrieval" exceeds the end point of the naphtha range, eg, the end point of the unstabilized wild straight naphtha range, but as described above, per unit operation. Provided is a means for determining the division of a hydrocarbon-containing liquid that boils below a break point at which the rate of increase is high and the sulfur content begins to increase rapidly or exponentially.

In the specification and claims, the base "break point retrieval" or the basis "sulfur delimiter retrieval" exceeds the end point of the range of unstabilized wild straight naphtha with respect to the sulfur content of the fraction. , Means a hydrocarbon-containing liquid that boils below the break point. If the fuel product flow is formed from a combination of all untreated flows below the break point and all flows above the break point extraction selected to be added to form the combination, then the break. The points are selected so that the actual sulfur content of the combined fuel does not exceed the target sulfur content. In a modified example, fuel can be produced when the target sulfur content is at the sulfur break point, or is higher or lower than the sulfur break point, and the combination of flows that produce the fuel is that of the fuel. It is efficiently made based on the above break point so that the actual sulfur content does not exceed the above sulfur target.

Hydrocarbon-based feedstocks containing crude and high sulfur oils with relatively high sulfur, nitrogen and metal content are supplied for atmospheric and vacuum distillation, (1) light overhead distillation gas, (2) below the sulfur delimiter. Liquid fractions, (3) (A) distillation range fractions containing sulfur, (B) reduced pressure light oil range fractions containing sulfur and (C) fractions above the sulfur break point with reduced pressure residues containing sulfur. , And (4) Distillation Units Separated into sulfur-containing purge gases such as distillation gases, strippers and other unit operating overheads containing small amounts of sulfur. The liquid fraction below the sulfur break point is supplied to the combination zone as an untreated liquid to form at least a portion of the fuel. The distillation range fraction and the reduced gas oil range fraction are brought into contact with the added hydrogen under the hydrogenation treatment conditions in the presence of a catalyst in a distillation and reduced pressure gas oil hydrogenation treatment apparatus to produce one or more hydrogenated liquids. Form. The hydrotreated liquid is sent to a combination zone and a purge gas having sulfur. The reduced pressure residue is sent to the boiling residue hydrogenation conversion zone, contacts the added hydrogen under boiling hydrogenation conversion conditions in the presence of a catalyst, and is supplied to (1) the combination zone to form a part of the fuel. Another treatment liquid, (2) purge gas with sulfur, and (3) soluble deasphaltated oil fed for solvent separation and (A) either alone or in combination with decompression residues for residual hydrogenation conversion. And (B) unconverted oil, which forms an insoluble pitch, sent to the pitch process. The untreated liquid is combined with the treated liquid to form a fuel whose actual sulfur content is less than or equal to the target sulfur content. Preferably, at least one of the hydrogenation streams is an ultra-low sulfur stream having sulfur of 10 ppm by weight or less, and the actual sulfur content can be increased by increasing or decreasing the amount of the stream with respect to the combination. The above fuel is formed by adjusting the sulfur content to be less than or equal to the target sulfur content.

In a modified example of the method of the present invention, the crude oil except for (i) a light overhead distillation gas of the distillate, (ii) pitch and (iii) a hydrocarbon composition having a hydrocarbon in sulfur or metal recovery vapor. Substantially all hydrocarbon compositions of feedstock can be separated into each fraction and then recombined to form the fuel, which is a single liquid fuel product rather than multiple hydrocarbon products. it can. The fuel is treated with hydrocarbons in the range from the lowest boiling point of the untreated liquid fraction from atmospheric distillation to the highest boiling point of the flow recovered from solvent separation, followed by a hydrogenation or hydrogenation conversion reactor. It can have a combination with a stream that is collected, recovered and incorporated into the fuel. In one variant, at least one of the hydrotreated steam is an ultra-low sulfur stream with less than 10 wt ppm sulfur, and the untreated fraction has a sulfur content that exceeds the target sulfur content. When the untreated fraction is used as a trim control, reducing or increasing the amount of such untreated fraction for the combination forms a fuel whose actual sulfur content is less than or equal to the target sulfur content. .. In another variant, the first hydrogenation treatment stream is made as a stream with a reduced sulfur content with a sulfur content of less than 10 wt ppm and the second hydrogenated fuel fraction has a sulfur content of 0. Made as a stream with a reduced sulfur content in the range of .12 to 0.18 wt%, the untreated fraction has a sulfur content that exceeds the target sulfur content and is the first hydrogenation treatment. A stream, a second hydrogenation stream, or both, is used for trim control to form a fuel whose actual sulfur content is less than or equal to the target sulfur content by increasing or decreasing the amount of such stream with respect to the combination.

In one variant, the residue hydrogenation conversion and hydrogenation treatment zones have separate distillation hydrogenation treatment reactors, heavy oil hydrogenation treatment reactors and residue hydrogenation conversion reactors, each of which is separate. Forming treated effluents, each treated effluent is fed to a separate shared wall separator, forming a common overhead gas with sulfur and reducing one or more separately associated with each reactor treated effluent. The gas-liquid treated effluent was separately removed from the separator at a rate based on each sulfur content and sent to (a) in combination with the untreated liquid stream, where the actual sulfur content was the target sulfur content. It forms a fuel that is less than or equal to the amount, or is (b) sent to pre-storage for subsequent trim control of the sulfur content of the fuel. In certain variations of the method of the invention, the amount of output product fuel may exceed the total amount of input feedstock, at least in part due to the volume increase caused by the addition of hydrogen.

These novel methods can adjust the sulfur content of the combined fuel to meet the target sulfur content within the IMO specifications for marine fuels or the turbine manufacturer's specifications for combustion gas turbines. Therefore, the fuels are particularly useful for offshore or land engines, combustion gas turbines or combustion heaters. Certain fuel variants derived by combining light tight oil and high sulfur fuel oil treated by residual hydrogenation conversion have an actual sulfur content of less than 0.5% by weight and crude oil derived hydrocarbons. A fuel in the range of about C5 to C20 or higher is produced. The hydrocarbon has an initial boiling point, which is the lowest boiling point of any fraction in the untreated stream combined with the fuel, and a highest boiling point portion of the effluent from solvent separation, followed by hydrogenation. Alternatively, it is treated by hydrocarbon conversion and combined to form part of the fuel.

FIG. 1 outlines one embodiment of the present invention and simplifies the main components of a method for converting a hydrocarbon feedstock containing sulfur and a metal to form a fuel. The light tight oil feedstock 1 is preferably passed through a basic gas-liquid separator prior to manufacture, shipment or other handling to separate or stabilize light companion gases, or to remove water and precipitates, or Receive other minor adjustments. The light tight oil feedstock 1 contains a relatively light and intermediate range of hydrocarbons with a relatively small amount of sulfur and metal and a relatively small amount of heavy oil and is combined as an untreated liquid stream without additional treatment Zone 600. Provided to. The high sulfur fuel oil having sulfur, nitrogen and metal is supplied to the residue hydrogenation conversion zone 401 via the line 41 and the residue hydrogenation conversion of a boiling bed reactor or the like selected based on the feedstock composition. A reaction in which the oil 41 is brought into contact with hydrogen in the presence of a catalyst in a vessel or other suitable hydrogenation conversion device under residual hydrogenation conversion conditions, and the zone 401 is divided into (1) treated hydrogenation conversion liquid 411. Container-classified effluent (in this specification, the "hydrogenation conversion liquid" referred to as the type of treatment liquid contains substantially the entire range of hydrocarbons from the boiling range of about C5 to the minimum boiling point of unconverted oil 409. It forms a hydrogenation conversion residue, a purge gas 420 with purged hydrogen and off-gas, a component of liquid petroleum gas, and an acidic gas with sulfur) and (2) unconverted oil 409. Such separation is preferably in the form of vacuum distillation, and in the case of certain feedstocks, distillation close to atmospheric distillation may be effective in separating unconverted oils. The unconverted oil 409 is supplied for solvent deasphaltification in Zone 301. The solvent de-asphalated separation 301 forms (A) soluble de-asphalated oil 311 and is a high sulfur fuel oil that is added separately or to the above reactor as a feedstock to the hydrogenation conversion reactor in zone 401. It is recycled in combination with the feedstock 41. The solvent deasphalted separation 301 also forms an insoluble pitch 351 supplied to the pitch treatment in (B) Utility Island 501. In the modification shown in FIG. 1, the pitch 351 is supplied to the utility island 501 and processed. In this embodiment, the pitch is burned in one or more gasifiers (not shown) to capture power and at least a portion of the metal removed in the hydrogenation conversion and gasifier solids. Can produce at least a portion of the hydrogen for.

The untreated liquid of line 1 is combined with the treated liquid 411 to form fuel in the combination zone 600. The fuel 600 is a high sulfur fuel in which the light and intermediate range hydrocarbons (i) of the light tight oil feedstock, condensate or other light feedstock 1 are present together with the treated liquid effluent 411 in the hydroconversion zone 401. Combined with many of the heavier range hydrocarbons (ii) of oil 41, the fuel 600 has a wide range of hydrocarbons C5 to C20 or higher. The fuel thus formed has a wide range of hydrocarbons, from the lowest boiling point of the light tight oil forming the fuel to the highest boiling point of the hydrocarbon of line 311 dissolved in solvent separation 301. Then, it is treated with hydrogen in the zone 401 to form a part of the effluent 411 for forming the fuel. The amounts and flow velocities of the compositions 1 and 411 can be adjusted based on their respective sulfur contents so that the actual sulfur content of the fuel 600 is less than or equal to the target sulfur content. For example, if, but not limited to, stream 1 has an unacceptably elevated sulfur content and cannot be used for combination within zone 600, the untreated stream 1 is fractionated (separated). (Not shown), any higher sulfur content heavy bottom portion can be sent to the integrated hydrogenation system within Zone 401 for treatment, leaving the rest of Flow 1 untreated in the combined zone. It can pass through 600. However, the extraction of higher sulfur content resulting from the treatment upstream of the hydroconverter, for example, the bottom of atmospheric distillation, is hydrocracked under hydroconversion conditions, unnecessarily consuming hydrogen and essentially light. It is not supplied to the hydroconversion as part of the flow 41 because it produces the lighter material present in the tight oil feedstock. Instead, such higher sulfur removal is sent to a separate hydrogenation zone, as shown in the variants below. In this variant, the production zone effluent treated by one or more reactors in zone 401 can be separated into two or more hydrogen conversion liquid fractions by fractional distillation, at least one such fraction. If one has a sulfur content higher than the target sulfur content, such fractions alone or with other streams having similar sulfur content and boiling range from outside Zone 401. Sulfur content reduced, preferably 0.5% by weight or less, sent to one or more separate hydration treatment zones within zone 401 and in contact with hydrogen under hydration treatment conditions in the presence of a catalyst. , More preferably 0.2% by weight or less of the hydrotreated stream, and the low sulfur hydrotreated stream remains from the untreated stream from the lighttight oil or the fractional distillation or other treatment of the lighttight oil. Combined with the current flow, it forms a fuel with an actual sulfur content below the target sulfur content. In one variant, the in-series or integrated hydrogenation system is 10 ppm by weight or less, depending on the amount of ultra-low sulfur or low-sulfur treated liquid required for the combined flow having a sulfur content below its target sulfur content. Yields a sulfur content of 0.1% by weight.

In the modified example of the residue hydrogenation conversion system 401 shown in FIG. 1, the constituent hydrogen-containing gas 502 in the amount required for hydrogenation conversion from the utility island 501 gasification system is inside the residue hydrogenation conversion block 401. Effective operating temperature, pressure, space known in the art to achieve the desired level of hydrogenation conversion, along with recycled hydrogen, compressed, heated and based on selected catalysts and other conditions. Adjusted to speed and pressure. The effluent and hydrogen-containing gas of the Zone 401 reactor having the treatment liquid may be separated by a high-pressure separator (not shown), recovered in Zone 401, and optionally sent to fractional distillation. The hydrogen-containing liquid is recovered. Purge gas with sour and acid gas is supplied via line 420 to Utility Island 501, which has a pitch treatment and sulfur recovery system. Pitching can have combustion in one or more boilers to produce electricity and steam, alone or with diluents, and in some cases sulfur from flue gas and other process gases. And ancillary equipment for removing or reducing metal and a hydrogen generating unit with a pressure swing absorption unit can be used. In another variant, pitch processing is by transfer for asphalt production or use as a coke feedstock for raw coke production. In yet another variation, the pitch is burned in one or more gasifiers to generate at least a portion of the metal for power generation, hydroconversion or hydrotreating and in the gasifier solid. Produce at least a portion of hydrogen to capture for metal removal through such solids. The optimal choice of how to handle the pitch depends on the amount of pitch produced, the effectiveness of the low cost hydrogen source, and the potential sales channels for the pitch.

Although not shown in FIG. 1, various auxiliary high, medium and low pressure gas-liquid separators, vapor heaters, gas reuse and purge lines, reflux drums for separating gas or light components from liquids. , Compressors, cooling systems, and other ancillary applications are known to those skilled in the art in the field of hydroconversion technology. Also, if not located within the common Utility Island 501, within the hydroconversion zone 401 may include various amine or other sulfur recoverant absorbers and stripping systems for sour gas or acid gas treatment. Let's go.

The parameters for the selection of the residue hydrogenation conversion catalyst and the adjustment of the process conditions of the residue hydrogenation conversion zone 401 are within the technical scope of those skilled in the art of the oil refining industry, and the residue hydrogenation conversion of the present invention. No additional explanation is required for the implementation of the division. Residue hydrocarbon conversion catalysts used in the reaction zones are heavy for increasing hydrogen content and / or removing sulfur, nitrogen, oxygen, phosphorus, Conradson carbon and metal heteroatomic contaminants. Includes any catalytic composition useful for catalyzing the hydroconversion of hydrocarbon feeds. The particular catalyst type and various supports and particle size configurations used and the residue hydroconversion conditions selected are as well as sulfur and metal content and heavy carbon residues, respectively from recovery or other streams. Hydrogenation of feedstock Depends on the feedstock composition, the desired reduced sulfur and metal content in the product flow from the reactor. Such catalysts can be selected from any catalyst useful for the residue hydrogenation conversion of hydrocarbon feedstocks. Patent Document 6 (2014) by Baldassari et al., Incorporated by reference herein, describes a wide variety of suitable residues, along with suitable residue hydrogenation conversion steps, including various integrated residue hydrogenation conversion devices. The hydrogenation conversion catalyst is also described. Baldassari et al. Further summarize the various catalytic compositions and condition ranges for distillation and hydrogenation conversion of heavy oil residues, and distinguish the conditions for hydrogenation conversion. All of these are known to those of skill in the art in the art of residual hydrogenation conversion. In a preferred embodiment of the present invention, the boiling bed hydrogenation conversion is carried out in a reaction temperature range of 380 ° C. to 450 ° C., a reaction pressure range of 70 bar to 170 bar (hydrogen partial pressure), preferably a liquid space velocity range of 0.2 to 2. Performed at 0.0h ^-1 , the conversion to 550 ° C. minus is in the range of 30% to 80%.

In another preferred variant, the pitch 351 is an integrated gasification with one or more gasifiers for partial oxidation of the pitch 351 in the presence of steam and oxygen, and any carbon-containing slurry quench. It is fed to the composite cycle system 501 to form syngas, at least part of which is converted to hydrogen and syngas, similar to the formation of high temperature turbine gas, which hydrogen is converted to gasification conversion system 401 via line 502. Syngas is used to burn the gas turbine of the combined cycle power unit in the Utility Island System 501 for power generation within 504 for process and other applications. The integrated gasification-combined cycle system 501 further has a heat recovery generator, recovers heat from high temperature turbine gas, etc., produces steam extracted through the use of line 507 internal processes, or drives a steam turbine. Then, it is directed to additional power generation as power via 504. Each gasifier also produces metal-rich soot. The soot may be in the form of granular solids and has high sulfur fuel oils and / or metal contaminants from heavy feedstocks. The solid is sent from each gasifier via line 506 for metal removal. The support system has one or more gas treatment units for sulfur removal via 508, regardless of whether all sulfur-containing gas streams from all unit operations are sour gas or acid gas. Is supplied to the above gas treatment unit. Preferably, such a sulfur removal system is part of a utility island of which the gasification system is also a part. More preferably, one or more sulfur-containing gas streams are used for commercial sulfur acid production as part of the overall sulfur removal. The gasification system within the utility zone 501 typically has an acid gas treatment optimized in capacity and configuration to produce the required hydrogen from at least a portion of the source synthetic gas produced within the gasification system. It has a unit and an acidic CO shift system.

In the embodiment of the method of the present invention shown in FIG. 2, the liquid flow 411 from the high sulfur fuel oil supply material 41 is combined with the liquid flow 15 from the light tight oil supply material 3 in the combination zone 600, and the actual sulfur content Produces fuels that are below the target sulfur content.

The light tight oil enters the process of line 3 and goes to the separator 101, where the feedstock 3 has at least two fractions, (a) at least a portion of the naphtha range hydrocarbons in the light tight oil feedstock 3. It is separated into an upper zone extraction 5 containing all of the lighter low hydrocarbons and a bottom containing (b) substantially outside the range of (a). The bottom 11 of the separator 101 is supplied to the combination zone 600 via lines 11 and 15 to form part of the product fuel. The upper zone naphtha and lower take-out 5 (i) pass through a separator (not shown), pass through line 7, and are used as process fuel or light distilled gas for internal use as capture or for other purposes. And (ii) have a flow 9 which is mainly a naphtha range hydrocarbon. After removal of the light gas, all or part of the flow 9 is sent directly to line 15 for direct combination (via connectors, lines 9 and 17 not shown) to form part of the fuel in zone 600. Alternatively, in consideration of the flash point of the combination 600, at least the low ignition portion of the flow 9 is passed through a processing unit 151 such as a conventional aromatic oil composite having a catalyst reformer well known in the essential oil technology field, and the flow 9 is passed. Is contacted with a catalyst in unit 151 to produce by-product hydrogen 505 and light treatment stream 155 recovered via line 159 for non-fuel or other applications. Unit 151 may be manufactured in a useful by-product, eg, liquefied petroleum gas 153, which is used internally as a process fuel or captured for other uses.

In FIG. 2, the high sulfur fuel oil enters the process through line 41, alone or with other heavy residues or superheavy oils, and is fed to the residue hydrogenation conversion zone 401 with very low sulfur. The liquid flow 41 is manufactured. As mentioned above in FIG. 1, the parameters for the selection of the residue hydrogenation conversion apparatus and the adjustment of various process conditions of the integrated residue hydrogenation conversion zone 401 are within the technical scope of those skilled in the oil refining industry. No detailed description of the implementation of the residue hydrogenation conversion classification of the present invention is required. In the illustrated modification of this embodiment, the integrated zone 401 has a hydrogenation conversion reactor, and the high sulfur fuel oil and other heavy feedstock in 41 are supplied to the reactor. Such a heavy feedstock 41 is preferably treated in a residue hydrogenation conversion zone 401 having a boiling bed reactor and separated into (1) a treatment liquid 411 and a purge gas 420 having hydrogen and sulfur. Reactor classification spillage and (2) unconverted oil 409 are formed. The unconverted oil 409 is supplied to the solvent separation 301. The solvent separation 301 forms (A) soluble deasphaltated oil 31 and is combined as a feedstock to the reactor 401 separately or in combination with the high sulfur fuel oil feedstock 51 added to the solvent separation zone 301. And be collected. The solvent separation 301 also forms a substantially insoluble metal rich pitch 351 which is the embodiment shown in FIG. 2, which is supplied to (B) pitch processing.

In the utility modification shown in FIG. 3, the pitch 351 is supplied to the boiler and burned to generate steam for steam turbine power generation 561. At least a portion of the boiler effluent 429 is of sulfur capture and removal, eg, via line 565, separately or with purging from the hydrogenation conversion zone 401 or with the hydrocarbon conversion zone 401 acid gas 420 in another gas stream. Through various amine or other sulfur recoverant absorbers and stripping systems for sour gas or acid gas, and in a variant, via a separation system for trapping and removal of metals via line 563, zones Processed within 701. Although not shown in FIG. 2, various auxiliary high, medium and low pressure gas-liquid separators, flow heaters, gas reuse and purge lines, reflux drums for separating gas or light components and liquids, Compressors, cooling systems, and other ancillary equipment are known to those of skill in the art of hydroconversion and hydrotreating. In the illustrated variant, in addition to any by-product hydrogen 505 from the process unit 151, other constituent hydrogen supplies to zone 401 are from the hydrogen generating unit 517 with the hydrogen source 519 via lines 503 and 509. A natural gas supply steam cracker, such as, but not limited to, having a pressure swing absorption unit can use at least a portion of the boiler steam from the utility zone 501 described below.

The combined heavy residue feed material to the hydrogenation conversion reactor zone 401 was brought into contact with hydrogen in the boiling bed reactor in zone 401 under the residue hydrogenation conversion conditions in the presence of a catalyst (1). It forms a reactor compartmentalized effluent separated into a treatment liquid 411 and a purge gas 420 with hydrogen and sulfur, and (2) unconverted oil 409. Also, various amine or other sulfur recovery agent absorbers and stripping systems for sour gas or acid gas treatment are contained in hydrogenation conversion zone 401 or separate sulfur recovery zone 701, to which the high sulfur purge gas 428 is supplied. Sulfur. The product fuel is formed by supplying the treated steam 411 to the combination zone 600, combining it with the untreated flow 15, and forming a combination so that the actual sulfur content is equal to or less than the target sulfur content.

In the embodiment of the method of the present invention shown in FIG. 3, the stream of contaminated crude oil containing sulfur, nitrogen and metal enters the treatment via line 2 after pretreatment such as desalting suitable for crude oil. In this embodiment, the crude oil feedstock 2 can be a single crude oil, a mixture of one or more crude oils, or a residual oil of the crude oil and a light tight oil or a high sulfur fuel oil, or a mixture of both. .. In the illustrated modification, the crude oil supply raw material 2 and the light tight oil supply raw material 3 are separately supplied to the atmospheric distillation column 100. Preferably, the light tight oil 3 is supplied to or near the upper portion of the crude oil 2 in the feedstock passage zone of the column 100, and the feedstock is separated into a light overhead gas 4 and a plurality of extracts. The light overhead gas 4 contains a non-condensable distilled gas 6 useful as a process fuel or is captured for other uses. In one preferred variant, the investment associated with the stabilization system for such overhead gas 4 is avoided. However, according to local needs, such as special marine fuel maximum H _{2 S} specification will include stabilization system.

In the embodiment shown in FIG. 3, the plurality of extracts are (1) unstabilized wild straight naphtha of line 16 via line 4, (2) sulfur break point extraction of line 18, and (3) line. One or more of 24 light fractions, (4) intermediate distillate of line 26, (5) first heavy distillate of line 28, and (6) atmospheric residue of line 30. May include flow. Preferably, the combination of sulfur break point flows (1) the unstabilized wild straight naphtha of line 16 via line 4 and (2) the sulfur break point extraction of line 18 is 0.06% by weight to 0. If the fuel combination 600 contains less than .08% by weight sulfur, the target sulfur content of the fuel combination 600 is less than or equal to 0.1% by weight, and the sulfur content of the treatment stream is less than 10% by weight, the combination is untreated. The flow rates of the steam 10 and the treatment streams 65, 75 and 85 are adjusted so that the fuel combination 600 does not exceed the target sulfur content. In a variant, the untreated low sulfur low metal light tight oil stream is fed directly to the combination 600 via line 53 in addition to the combination of lines 10, 65, 75 and 85 to the final sulfur content and combination zone. Adjust the other parameters of 600.

In FIG. 3, the atmospheric residue is supplied to the vacuum distillation column 200 via the line 37, alone or together with the residual oil supply material 35 to which a high sulfur fuel oil or the like is added, and is supplied to the vacuum distillation column 200 (1) at the line 32. Distillation, (2) light decompression gas oil on line 36, (3) heavy decompression gas oil on line 38 and decompression residue on line 50. The reduced pressure residue 50 is sent to the integrated residue hydrogenation conversion and hydrogenation treatment zone 401 via lines 57 and 317, alone or with the added residual oil 55 such as high sulfur fuel oil.

Parameters for the selection of integrated residue hydrogenation conversion and hydrogenation treatment equipment and catalysts and the adjustment of various treatment conditions within the integrated residue hydrogenation conversion and hydrogenation treatment zone 401 are those skilled in the oil refining industry. It is within the technical scope of the present invention and does not require a detailed explanation of the implementation of the residue hydrogenation conversion and hydrogenation treatment classification of the present invention. In the illustrated variant of this embodiment, the integrated zone 401 is (A) added with the heaviest and most contaminated feedstock via lines 57 and 317, eg, via reduced pressure residue 50 and line 55. Hydroconversion reactor zone 490 to which the high sulfur fuel oil and other heavy feedstock are supplied, (B) the heaviest distillate and light oil are delivered via line 39, eg, (1) line 36. Light decompression light oil and (2) line 38 heavy decompression light oil are supplied and separated from the hydroconversion reactor effluent in zone 410 by, for example, vacuum distillation of the reactor liquid product stream. Heavy oil hydrotreated reactor zone 460 to which the decompressed oil is supplied, and (C) a lighter and less polluted feedstock via line 20, for example, (1) the light distilled content of line 24, (2). It is supplied via the intermediate distillate of line 26, (3) the first heavy distillate of lines 28 and 32, and (4) the line 29 having the second heavy distillate, and flows out of the hydrogen conversion reactor. It has a distillation hydrotreated reactor zone 430 to which the distillation range material separated from the material into zone 401 is supplied. For example, the second heavy distillate of line 32 can instead be supplied to the heavy oil hydrotreating apparatus 460 depending on the line 32 composition and loads on the hydrotreating apparatus reactors in zones 430 and 460. It is necessary to balance and control the sulfur content level. In such an integrated residue hydrogenation conversion and hydrogenation treatment zone 401, the reuse and constituent hydrogen streams 410 and 414 and the purge gas streams 412 and 416 are integrated reuse, separation and removal known to those skilled in the art of essential oil technology. Have a system. Although not shown in FIG. 3, various auxiliary high, medium and low pressure gas-liquid separators, flow heaters, gas reuse and purge lines, reflux drums for separating gas or light components and liquids, Compressors, cooling systems, and other ancillary equipment are known to those skilled in the art in the field of hydroconversion and hydrotreating techniques. In the illustrated modification, the hydrogen supply 503 is performed from the hydrogen generation unit 517 having the hydrogen source 519, and for example, the natural gas supply vapor decomposition apparatus having the pressure swing absorption unit is described in the utility zone described later. At least a portion of the boiler steam from 501 can be used.

The heavy residue feedstock 317 combined with the hydrogenation conversion reactor zone 490 was brought into contact with hydrogen in the boiling bed reactor of zone 401 under the residue hydrogenation conversion conditions in the presence of a catalyst, and (1) first. 2 By a vacuum distillation unit (not shown), preferably (1) (i) naphtha, (ii) intermediate distillation and (iii) treatment liquid 85 with reduced pressure light oil, purge gases 416 and 428 with hydrogen and sulfur. It forms a reactor-classified effluent that is partially and (2) separated into unconverted oil 409. Also, various amine or other sulfur recovery agent absorbers and stripping systems for sour gas or acid gas treatment are contained in hydrogenation conversion zone 401 or separate sulfur recovery zone 701, to which the high sulfur purge gas 428 is supplied. Sulfur. As is known in the art, during processing in a hydrogenation conversion reactor 490 boiling bed containing a metal and / or other contaminants deposited on the boiling bed, or in the boiling bed of reactor 490. At least a portion of the other material accumulated with the catalyst is removed via line 421 and replaced with a constituent catalyst via line 423. In one variant, the processing liquid 85 with (i) naphtha, (ii) intermediate distillation and (iii) reduced gas oil is fractionated, the intermediate distillation is sent to the distillation hydrogenation treatment apparatus 430, and the reduced gas oil is It is sent to the heavy oil hydrogenation treatment apparatus 460.

The hydrogenated unconverted oil 409 is sent to the solvent separation 301. The solvent separation 301 may be added to the (A) vapor hydrogenation conversion reactor 490 or zone 460 in other variants, either separately or in combination with the reduced pressure residue 50, if the high fuel oil feedstock 55 is added. , Forming soluble deasphalized oil 311 supplied via lines 57 and 317 to the hydrogenation conversion reactor 490. The solvent separation 301 also forms the insoluble metal rich pitch 351 supplied to the pitch treatment in (B) Utility Island 501. In the utility variant shown in FIG. 3, the pitch 351 is sent to the boiler, where the pitch is burned to generate steam for steam turbine power generation 504, where at least part of the boiler effluent 429 is separated within zone 701. In or with Zone 401 Acid Gas 428, for example treated with various amines or other sulfur recovery agent absorbers, vapor trapping and removal via line 561 by a sour gas or acid gas stripping system, and line 563 by a separation system. The metal capture and removal process is performed via.

In the modified example shown in FIG. 3, the sulfur content of the fuel product 600 is controlled as follows below the target sulfur content limit level. (A) Unstabilized Wild Straight Nafsa 16 and Sulfur Demarcation Point Extraction 18 are fed to the combination 600 via line 10 without any additional treatment of any such flow, followed by (B) Actual product sulfur level 600 to (1) one or more of the streams of light distillate 24, intermediate distillate 26, first heavy distillate 28 and second heavy distillate 32. Or increase or decrease the amount of, or add or reduce the intermediate distillation in the hydroconverter reactor effluent formed in the integrated zone 401 to the distillation hydrogen treatment apparatus zone 430, or (2) light decompression. Increase or decrease the amount of flow 39 with light oil 36 and heavy decompression light oil 38, or distiller effluent depressurized light oil (not shown) formed in integrated hydrotransformation (401) to heavy oil distillation apparatus. A line formed from (c) (1) light distillate 24, intermediate distillate 26, first heavy distillate 28 and / or second heavy distillate 32, added or reduced to 460. Flow from Distillation Hydrotreat Zone 430 via 65, and any hydride converter effluent intermediate distillate, (2) light decompression light oil 36, heavy decompression light oil 38 and any hydride converter effluent decompression Flow from heavy oil distiller zone 460 through line 75, formed from light oil, or (3) naphtha and hydride if for some reason the actual product 600 sulfur level needs to be increased to the target sulfur level. Reduce the amount of one or more of the other treated liquid effluents 85 from the conversion reaction zone 490 to the combination 600, or (d) (1) via line 65 from the distillation hydrotreat device 430. Hydroconversion if the above flow, (2) flow through the line from the heavy oil distillation apparatus 460, or (3) for some reason the actual product 600 sulfur content needs to be reduced below the target sulfur limit level. The amount of processing flow from the reaction zone through line 85 to one or more of the combinations 600 is increased. Due to such promotion, for example, fuel supply for sulfur fuels of 500 wt ppm or less for offshore and onshore gas turbines, and different for different end consumption sites requiring different target sulfur contents in the same application. Efficient production of multiple sulfur grades, such as range.

In a variant using a high sulfur fuel oil having a sulfur content higher than the target sulfur content limit level of the final fuel in combination 600, the high sulfur fuel oil is one of a variety of feedstocks. As a unit, it is supplied to one or more unit operations. Depending on its sulfur content, high-sulfur fuel oil remains on (a) supply line 2 to atmospheric distillation 100 or line 30 to vacuum distillation 200 and (b) via lines 55, 57 and 317. Light distillate 24, intermediate distillate 26, first heavy distillate 26 or second added to physical hydroconversion reactor 490, (c) separately or to line 20 to distillate hydride treatment apparatus 430. In combination with one or more of the heavy distillation 32 feedstock, to the Distillation Hydrotreat 430, (d) separately or in combination with one or more of the light decompression gas oil 36 or the heavy decompression gas oil 38. Addition to line 39 to the gas oil hydrogenation treatment apparatus 460 or to solvent separation zone 301 via (e) line 59 forms a fuel combination 600 in which the actual sulfur content is less than or equal to the target sulfur content limit. be able to.

In another variant, the combined 600 zone clean fuel is a high sulfur fuel oil capable of having a sulfur content higher than the target sulfur content limit level, (a) high without any additional treatment. Flow 10, formed from unstabilized wild straight naphtha 16 and sulfur break point extraction 18, added depending on the sulfur content of the sulfur fuel oil, (b) wild naphtha and ultra-low sulfur diesel range material Formed from a stream 65 formed from a distillate hydrotreating apparatus 430 containing, or (c) a heavy oil hydrotreating apparatus 460 having a stream with wild naphtha, ultra-low sulfur diesel and a second reduced sulfur content. Addition to one or more of the stream 75, or (d) the treated effluent 85 from the hydroconversion reactor 85, and the treatment conditions and sulfur content of each stream of the treated streams 65, 75 and 85, as described above. It is formed by adjusting the actual sulfur content of the fuel 600 to be less than or equal to the target sulfur content limit, taking into account the sulfur content of the untreated steam 10, if any.

In a preferred embodiment in which high sulfur fuel oil is used in the preparation of the fuel composition 600, after measuring the sulfur content of such high sulfur fuel oil, the high sulfur fuel oil is used as part of the feedstocks 55 and 59. The fuel oil content of the treated liquid effluent 85 is adjusted to the above-mentioned high level by supplying one or more of the solvent separation unit 301 or the residue hydrocarbon reaction zone 490 as the above, optimizing the adjustment of the hydroconversion conditions of the zone 490 While determining by the sulfur content of the sulfur fuel oil, a fuel having an actual sulfur content of less than or equal to the target sulfur content limit is formed in the zone 600.

The flow sheets of FIGS. 1, 2 and 3 showing the various intermediate individual products are for the explanation and understanding of the major and by-products in the effluent of each unit operation depicted. Is. The selected variant of separation or processing by each unit operation depends on the optimization of the selected crude oil and feedstock, and the intermediate products produced to produce fuels with sulfur below the target specifications. For example, the respective treatment effluents 65, 75 and 85 shown in FIG. 3 from the hydrogenation treatment apparatus 430, 460 and the hydrogenation conversion reactor 490 are integrated by the use of a common gas-liquid separator (not shown). Can be combined within zone 401. For example, the ultra-low diesel produced in the hydrogenation treatment device 430 is not separated from the higher sulfur content hydrogenation treatment substances produced in the hydrogenation treatment device 460 or the hydrogenation conversion reactor 490, and all hydrogenation is performed. The processing materials 65, 75 and 85 are combined and fed into any one stream to the combination zone 600. As mentioned above, the parameters for the integrated residue hydrogenation conversion and the adjustment of various treatment conditions within the hydrotreating zone 401 are within the skill of those skilled in the oil refining industry. For example, the conditions for hydrogenation conversion and hydrogenation treatment are adjusted more gently to avoid decomposition if you want to have less light parts in the mixture, and more severely if you want to have less heavy parts. It will be adjusted.

4 and 5 show a combination of one or more components having a novel fuel and a series of light (L), intermediate (M) and / or heavy (H) materials for forming such fuels. Teach the recipe.

FIG. 4 is a plot of both the temperature and density profiles relative to the volume fraction of the reference fuel produced by the method of the invention, and its (L), (M) specified as taught herein. ) And (H) are shown.

FIG. 5 shows the temperature and density profiles for the volume fraction of the reference light condensate that can be used as the "barrel top" for the combination. That is, such a condensate has most of the naturally occurring components of (L), with a small amount of naturally occurring (M) and (H) 1. The selected condensate is combined with additive (H) 2 from other sources such as the "barrel bottom" to constitute the fuel of the present invention.

FIG. 5 teaches, by way of example, that the stock material in a refinery's “warehouse” for selecting possible combinations is rather large, but the recipes for the choices taught herein are not. ..

The essential requirement is that if the fuel of the present invention is formed by combining a series of hydrocarbon components, (L), (M) and (H), the resulting combination will be based on a total volume of 100% by volume: Is to be decided.
(A) (L)% + (M)% + (H)% = 100%,
If (b) (L)% = (H)% = (100%-(M)%) / 2) and (c) (M)% are zero (zero) or less than 100%, the remaining ( The L)% / (H)% ratio is 0.4 / 1 to 0.6 / 1.
Such a combination has (1) a density at 15 ° C. of 820 to 880 kg / M3 or less, (2) a sulfur content of 0.25 wt% or less, and (3) a metal content of 40 ppm by weight or less. It has the characteristic of. As described herein, less sulfur and metals are preferred.

Potential ingredients of (L), (M) and (H) are industry compositions to allow those skilled in the art of essential oils to first know how to select the combination according to the recipe of the present invention. From a reference point of view, it is first summarized and then narrowed down by the restrictions of the above and below requirements.

For example, with respect to components in the "(L)" or "light component" range, the particular component may be within a variant found in a locally available refined "warehouse" or otherwise. May require manufacturing if not available locally. As a requirement herein, applicable (L) may include, but not all, components of naphtha and kerosene range material, for example, depending on the sulfur and density requirements for the fuel combination. As used herein and in the claims, (L) is below 38 ° C. (100 ° Fahrenheit), 90% plus end point 190 ° C. (374 ° Fahrenheit) to approximately 205 ° C. (Fahrenheit). It means the whole range of naphtha having (401 degrees). (L) is a fractional distillation, hydrogenation treatment or other treatment step other than (a) purification or partial purification, (b) unpurification, or (c) extraction and any separation of light gas or water. It can be used without doing it. For example, the specific component of (L) or the precursor of (L) is published to the industry-provided system Platts, but the range of materials provided is not based on sulfur breaks. This is because the break points are new and the treatment of materials added to the combination or low sulfur alternatives needs to be considered. Therefore, the description of the components below is a guide to where to refer.

Such applicable components of (L) are also, but not limited to, within the definition specified by the EIA (including the conversion from Fahrenheit to Celsius in parentheses) (i) "Naphtha: A general term for refined or partially refined petroleum fractions that boil in the range of approximately [50 ° C to 204.5 ° C] (122 to 401 ° F), and (ii) "naphtha: approximately [50 ° C]. A purified or partially purified light fraction having a boiling point in the range of ~ 204.5 ° C] (122 to 401 degrees Fahrenheit). It is further compounded or mixed with other substances to form high-grade motor gasoline and jet fuels. It is also used as a solvent and petrochemical raw material oil, and is used as a raw material for urban gas production. Therefore, when the teachings of the present invention are carried out in accordance with the requirements taught herein, one or more suitable (L) or light components are manufactured or procured, or such components are manufactured. Procurement of starting materials for this is known to those skilled in the art of refining technology. For example, the component (L) preferably has a sulfur content below or near the break point, which limits the fuel sulfur by the combined sulfur contents of (M) and (H). If it does not exceed, it may exceed the break point. It is preferable that the range of the heavier portion of (L) ends at the sulfur break point of the crude oil in which the (L) is produced.

Ingredients to which the "(M)" or "intermediate component" range used herein applies are, as all requirements herein, from about 190 ° C. (374 degrees Fahrenheit) to about 205 ° C. (Fahrenheit). It means a refined or partially refined petroleum fraction with an initial fraction of (401 ° C.), 90% plus end point of about 385 ° C. (725 ° F.) to 410 ° C. (770 ° Fahrenheit). However, the range of the lighter portion of (M) preferably begins at the sulfur break point of the crude oil in which the (M) is produced. The component (M) can include a bottom portion of light tight oil that is heavier than the naphtha range. In a preferred variant, as another requirement herein, the starting component of (M) has an intermediate distillate combination of hydrocarbons in the kerosene range of about 1/3 to the diesel range of about 2/3, and ASTM. It has a density in the range of 820-880 Kg / M3 at 15 ° C. according to D4052.

It is known to those skilled in the art of purification to manufacture or procure one or more suitable (M) or intermediate components when carrying out the teachings of the present invention in accordance with the requirements taught herein. is there. In many variants found within the available purification "warehouse", as (M), but not limited to, within the definition specified by the EIA, including the conversion from Chinese to Celsius in parentheses. ) (I) "Intermediate Distillate: Refined Petroleum Product Containing Distilled Fuel Oil and Kerosene in General Classification", boiling below 385 ° C (725 ° C), (ii) "Kerosene: Space Heater, Cooking Light petroleum distillation and kerosene, which are used for stoves and water heaters and as a light source when burning with a core lamp, have a 10% recovery point maximum distillation temperature [204.4 ° C] (401 ° C) and an end point [300 ° C]. ° C.] (572 degrees Celsius), minimum flash point [37.8 ° C.] (100 degrees Celsius). Two grades No. 1-K, No. 2-K, and No. certified by ASTN standard D3699. .1 Contains other grades of kerosene called range oil or stove oil, which have similar properties to fuel oil ", (iii)" Light light oil: approximately [205 ° C to 343.8 ° C] (401-650 ° C) 385 of "Liquid petroleum distillate heavier than naphtha boiling in the range of)" and (iv) "Heavy light oil: Petroleum distillate boiling at approximately 343.8 ° C to 537.8 ° C (651 to 1000 ° C)" The (iv) portion that boils below ° C. (725 ° C.) can be mentioned, and it is required that only the portion that boils below 385 ° C. (725 ° C.) is included in (M). (M) is also a material (v) "kerosene jet fuel", (vi) "No. 1 distillate", (vii) "No. 1 diesel fuel", (viii) "No. 2" within the EIA definition. "Distillate", (ix) "No. 2 diesel fuel", (x) "No. 2 fuel oil", (xi) "distilled fuel oil" and (xi) No. if possible. 4 Fuel or No. 4 All of the above, including some of the diesel fuel, are required to boil below about 385 ° C (725 ° F). The EIA broadly includes diesel fuels as "diesel fuels: formulations having residual oils as fuels consisting of distillations obtained in petroleum refining operations or formulations of such distillations with residual oils used in automobiles. Diesel fuel has a higher boiling point and specific gravity than petroleum. " Thus, since the residual oil is in a substance defined as diesel, whether a diesel is (M) or (H), based on the factors taught by the present invention by those skilled in the art of essential oils. Please be evaluated. Many diesels, as defined by the EIA as "high sulfur diesel (HSD) fuels: diesel fuels containing more than 500 ppm sulfur", are subject to (M) due to other requirements of the invention, as further described herein. ) Or (H). However, as defined by the EIA, "low sulfur diesel (LSD) fuel: diesel fuel containing sulfur exceeding 15 ppm but not more than 500 ppm" and "ultra low sulfur diesel (ULSD) fuel: diesel fuel containing up to 15 ppm sulfur". Applies to (M), but may fall under (H) due to other requirements of the present invention, as further described herein.

According to other requirements described herein, the essential attributes of the (M) component range can form part of the combinations of the invention having a combination density of 820-880 kg / M3 at 15 ° C. The (M) standard (often referred to as bulk) density for such a range should be 820 kg / M3 to 880 kg / M3 at 15 ° C. That is, even if the individual components of (M) are outside the range, the aggregate of (M) corresponds to 820 to 880 kg / M3 at 15 ° C.

In the modified example, the (M) component range has a higher sulfur content than the pre-treatment break point, such as the hydrogenation treatment described herein for the removal of sulfur. However, except in limited cases where the (M) component may be above the break point, the treated (M) such as the hydrotreat effluent is treated as the hydroconverter effluent. After treatment, the sulfur content when combined with (H) is adjusted so that the combination of (L), (M) and (H), both of which are combined with (L), does not exceed the fuel sulfur limit. (M) Sulfur content should be lower than the break point. Higher levels of the selected break point allow the maximum amount of material in (L) to bypass downstream treatments such as hydrogenation if used for sulfur removal, hydrogenation costs and other Reduce operating costs. In one variant, (M) is hydrogenated to produce a very low sulfur content in the range of about 10 ppm by weight and a very low or substantially metal free effluent. Specific hydrogenated materials of various grades that can be selected for use as components or precursors of (M) are published in Platts, a well-known industry-provided system. If (M) is absent or not added, then the boundary between (L) and (H) shall meet the requirements of (M).

The components of "(H)" or "heavy component" used herein are the first to be about 385 ° C (725 ° F) to about 410 ° C (770 ° F) as a requirement herein. It means a refined or partially refined petroleum fraction with a fraction, an end point below about 815 ° C (1499 degrees Fahrenheit). Such (H) end points are attributes of (H) components that can be known by acquisition studies or manufacturing tests. In one variant, the (H) end point is the highest boiling point of the components of the stream that are recovered from the solvent separation, subsequently treated by a hydrogenation or hydrogenation conversion reactor, recovered and combined to form the fuel. It is set according to the raw material oil such as and / or the processing conditions.

(H) One essential attribute of the component range is sulfur and certain heavy asphaltene and metals during production, eg, by treatment by solvent separation and / or hydrogenation conversion and / or hydrogenation as described above. Sulfur and metals in the fuels of the present invention are reduced to the proper amount of components treated to reduce the presence of hydrogen, or to levels that can be added to the combination of (L), (M) and (H). Another processing process that meets the specifications. Another essential attribute of the (H) range component is the (H) range density and contribution to the final fuel combination, and the density of the fuel combination at 15 ° C. according to the other requirements described herein. Is to enable the formation of some of the combinations of (L), (M) and (H) of the present invention, wherein is 820 kg / M3 to 880 kg / M3.

Therefore, when the teachings of the present invention are carried out in accordance with the requirements described herein, the manufacture or procurement of (H) or one or more suitable components of the heavy constituents, or the feedstock and it. The method for producing the above is known to those skilled in the art of essential oils. In many variants found within the available purified "warehouse", the starting material for the component of (H) is, but not limited to, within the definition specified by the EIA (i) (iii). ) "Heavy light oil: 343.8 ° C to 537.8 ° C (651 ° C to 1000 ° F)", the part of the petroleum distillate that boils above about 385 ° C (725 ° F). It is required that (H) contains only the portion that boils above 385 ° C. (725 ° F.). (H) also has an initial distillate of about 385 ° C. (725 ° C.), "heavy gas oil: petroleum distillate boiling approximately in the range of 651 ° C. to 1000 ° C.", ASTN standards D396 and D975 and federal standards. (Ii) Residual fuel oil according to VV-F-815C: No. remaining after distillation fuel oil and light hydrocarbons were distilled and removed by refinery operation. 5 and No. 6 Includes a general classification of heavy oils known as fuel oils. No. Reference numeral 5 is a medium-viscosity residual fuel oil, also known as Navy Special, which is defined in the military standard MIL-F-859E, including Amendment 2 (NATO Symbol F-770), steam from government agencies and coastal power plants. Used in power ships. The No. 6 fuel oil contains bunker C fuel oil and is used for power generation, room heating, ship bunker ring, and various industrial purposes. (Ii) EIA defines "No. 6 residual fuel oil".

FIG. 4 shows an embodiment of the composition of the fuel of the present invention produced by the method of the present invention.

FIG. 4 shows two profiles for volume fraction, temperature profile 602 and density profile 604, for the reference crude oil processed according to the present invention. That is, in FIG. 4, in both the upper chart and the lower chart, the x-axis 610 shows the volume fraction of crude oil. The y-axis 612 of the top chart shows the boiling points in degrees Celsius of the various extracts with the temperature profile curve 602 as data points. The y-axis 614 of the lower chart of FIG. 4 shows the density data of the reference crude oil on which the density profile curve 604 is drawn.

In both the upper and lower charts of FIG. 4, two vertical dotted lines LM606 and MH608 are drawn intersecting the temperature profile 602 and density profile 604 curves. The vertical lines LM602 and MH604 are depicted as volume fractions of the reference crude oil in the selected yield fractions (L), range 622 and (M) range 624. In FIG. 4, the intersection of LM606 is 205 ° C., the intersection of MH608 is 385 ° C., and the respective ranges of (L) 622 and (M) 624 are determined. For crude oils that are lighter or heavier than the reference crude oil, shift the line to the right or left.

Point 609 indicates the end point of the range (H) having decompressed gas oil cut up to 565 ° C and deasphaltated oil from the decompressed residue remaining below 565 ° C. It is understood that the temperature at point 609 depends on the rise in deasphalted oil and from point 609 100% by volume representing the pitch is not shown. The temperature point 611 is a treated (H) heavy decompression gas oil boundary point portion used for the combination and has (H) 626 portions from points 611 to 609, which are deasphalized oils. The corresponding density points are shown in FIG. 4 as 615 for the entire range of untreated crude oil. 613 is a straight line passing through the bulk densities of (L), (M), and (H) in the treated crude oil.

Therefore, the highest boiling end point in the (L) range 622 and the initial retention point in the (M) range 624 share a common vertical line LM606. The highest boiling point in (M) range 624 and the initial boiling point in (L) range 626 share a common vertical line MH608. (H) The actual end point 609 of the precursor to range 626 is shown in other embodiments of the invention and, as described in the definition of (H), a particular heavy asphaltene and other complex hydrocarbons. A cutting point for removing and substantially removing metals, leaving a very low amount of sulfur (H) that contributes to the final fuel.

FIG. 4 further shows (L) for forming a fuel composition that assumes the fuel of the present invention produced by the method of the present invention, which is disclosed herein with respect to the fuel produced by the method of the present invention. , (M) and (H) show how to combine the components. In the outline as an example of modification, the components are investigated, the density is plotted against the volume fraction, and the line 640 with the minimum density required at 15 ° C. and the line with the maximum density of 880 Kg / M3 at 15 ° C. Find the center point of the (M) range between 642. The center point 630 (the density pivot defined later) is the intersection of density vs. volume in the middle of the (M) range, ± 10% by volume or a very small or non-existent (M) range component. It is the attribution point where (L) ends and (H) begins there or in between. The black square 630 in the center is the center point of the bulk density in the (M) range, and 631 and 633 are the center points of the bulk density in the (L) range and the (H) range, respectively.

When a crude oil lighter than the reference crude oil is processed by the method of the present invention to prepare a fuel, the vertical lines LM606 and MH608 are shifted to the right, and the ranges (L) 622, (M) 624, and (H) 626 are lighter in composition. It means that the volume of the element (L) range 622 becomes large and the volume of the range (H) 626 becomes small. The density pivot 630 moves slightly and the fuel density decreases, but remains within the density fulcrum 632 (defined below). When heavy oil heavier than the reference crude oil is processed by the method of the present invention to produce fuel, the opposite occurs. That is, the vertical lines LM626 and MH628 are shifted to the left, which means that the volume of the component (H) is increased and the volume of the range (L) is decreased. Although the fuel density increases, the point of the fuel combination density pivot 630 remains in the 820-880 kg / M3 density zone between lines 640 and 642. In such an example of a lighter and heavier feedstock, a fuel having a bulk density within 820-880 Kg / M3 is supplied to the fuel combination density zone between lines 640 and 642 for the combination fuel. , (L) and (H) components (as well as (M) components, if any) are required, along with the aggregate required densities to balance each range of (L) and (H). is there.

Therefore, very light feedstocks, mainly in the (L) range, such as light tight oils and condensates, have a final product bulk density within the density fulcrum and a fuel combination density zone of 820-880 kg / M3. It does not have a sufficient amount of heavy material (M) or (H) to act as a single substance that fuels it.

As used herein and in the claims, (a) the term "density fulcrum" has a bulk density of 820-880 KG / M3 at 15 ° C. and a volume of approximately ± 10% at the density pivot. It means a density pivot (defined below) within the fractional range or a center located near it. For illustration purposes, but not limited, nominally 48% by volume is measured within 43-53% by volume and nominally 85% by volume is measured within 80-90% by volume. (B) The term "density pivot" means the center point of the density fulcrum, and when the components (L) and (H) of the same volume are combined, they are balanced with or without the component (M). Density can be achieved. All of the cited lines are at one end of the density curve 604, as both ends are within the 820-880 kg / M3 fuel combination density zone between lines 640 and 642 and the bulk density of the combination is at point 630. Whether the range is upward or downward, it passes through the required bulk density fulcrum, which serves as an essential guide for the above fuel formulations.

Observing the density profile 604 shown in FIG. 4, the (bulk) density extends almost in a linear profile, and although the fluctuation is small, it can be inclined outside the parallel zone range of the density fulcrum 632 and swivel near the center 630 of the density fulcrum. I understand. As shown, when the density range is 882-880 kg / M3 at 15 ° C., substantially equal volumes of (L) and (H) lift and rotate line 604 for the entire formulation. It falls within the bulk density range between 640 and 642 of the clean fuel of the present invention.

If the density of the final combination fuel product is lower than the minimum density of the density fulcrum 632 (eg, low density requirement less than about 820), the calorific value is reduced and the fuel consumption is reduced to achieve the equivalent energy effect. Need to increase. If the density of the final product exceeds the maximum density of the density fulcrum 632 (eg, top density requirements greater than about 880), problems arise with respect to engine fuel feedstocks, handling systems, and other end use.

If all other conditions are met, then (M) can be substantially reduced or eliminated without disturbing the balance of the density fulcrums, and still forming a satisfactory fuel of (L) and (H). It is amazing that it is possible. This allows the top and bottom of a particular barrel combination to recover the diesel range from (M) and still form a satisfactory fuel with the remaining (L) and (H).

FIG. 5 shows, for example, the method of the present invention using light tight oil as (L) range component "top of barrel" with other components as (H) "bottom of barrel". It shows how to form a fuel composition assuming the fuel to be produced.

In FIG. 5, the condensate is used as the reference light tight oil type material shown in the chart above FIG. This is an example of a light "barrel top" material with a 53 ° API, about 69% by volume (L) range 722 ending at line 706, and only 28% by volume (M) ending at line 708. ) 724 and about 3% by volume atmospheric residual bottom as part of (H) 1 shown as 726 contributing to the final combination. The yield curves 702 of the condensate reference material at various temperatures 712 plotted against the volume fraction 710 are shown in the chart of FIG. As described above, by this reference material analysis, as a general approximation, about 69% by volume (L) range 722, 28% by volume (M) range 724 and about 3% by volume (H) 1 range. Interpreted as 726. The end point 711 is 100% by volume because the bottom is a relatively light gas oil range material containing very little heavy residue. If the density fulcrum is shown for reference only (does not include added (H) 2 shown only in the chart below FIG. 5), about 85% of the volume fraction of the original reference without added (H) 2. Appears on the right side around. Therefore, in order to achieve a balance of combination curves within the density target range of 820-880 kg / M3 between line 740 and line 742, at least additional (M) range components, preferably (M) + ( The H) component, or more preferably the (H) range material, is required for the combination, along with the component of (M).

In this example shown in the chart below FIG. 5, each of the reference condensates naturally occurring as about 69% by volume (L) 722, 28% by volume (M) 724 and 3% by volume H1 range 726. To the barrel is added another source, eg, 0.69 barrel of (H) 2 non-condensate 727 produced as a full range effluent by hydroconversion. The black square 730 in the center is the (M) range bulk density center point, and 731 and 733 are the (L) range and the entire (H) range bulk density center points, respectively. The combination with Addition (H) 2 is assumed to be 1.69 barrels (100% by volume shown in the chart below FIG. 5 as (L) + (M) + (H) 1 + (H) 2). Forming the blended clean fuel of the invention, the fuel has a density of 820-880 Kg / M3, which is a requirement for a fuel product API of about 25-28, examples of which are shown in Table 1.

（配合燃料は、低硫黄及び金属仕様を満たす）

(Compound fuel meets low sulfur and metal specifications)

In yet another variation of the invention, the amount of M in the combination is reduced to near zero. This is due to the shortage of supply of diesel and other materials in the (M) range, which is required due to the ultra-low sulfur diesel route requirements and the high demand for low sulfur offshore and gas turbine applications. In this variant, for the formation of compound fuels, a combination of substantially equal (L) and (H) moieties is made that contains little or no (M). The choice of "heavier condensate" or light tight oil results in more atmospheric residue, and in some cases light oil range materials shift the vertical line (LM) to the left and are heavier. The density fulcrum rises as the density increases due to the contribution of light tight oil.

In one embodiment to which the above applies, we provide a novel blended fuel having a combination of one or more components consisting of (L), (M) and (H). Here, each amount with respect to 100% by volume of the total amount to be combined is determined as follows. (A) (L)% + (M)% + (H)% = 100%, (b) (L)% = (H)% = (100%-(M)%) / 2), and (c) ) When (M)% is zero or less than 100%, the remaining (L)% / (H)% ratio is 0.4 / 1-0.6 / 1, and the combination is (1). It is a fuel having a density of 820 to 880 kg / M3 at 15 ° C., (2) a sulfur content of 0.25 wt% or less, and (3) a total metal content of 40 wt ppm or less. In one modification, sulfur is reduced to 0.1% by weight or less and metal is reduced to 25% by weight or less. In one variant, 10% to 90% of (M) is present and the remaining (L) / (H) ratio is 0.4 / 1-0.6 / 1. In another modification, the existing (M) is 20% to 80%, and the remaining (L) / (H) ratio is 0.4 / 1 to 0.6 / 1. In yet another modification, 30% to 70% of (M) is present and the remaining (L) / (H) ratio is 0.4 / 1-0.6 / 1. In a simplified embodiment, (M) is in the range of 30% to 70% by volume and the rest has a substantial (L) / (H) ratio of 0.9 / 1-1 / 0.9. Consists of (L) and (H) parts equal to. In other embodiments, (M) is in the range of 40% to 60% by volume, the density at 15 ° C. is 820-880 kg / M3, sulfur is 0.25% by weight or less, and metal is 40% by weight ppm. It is as follows.

Therefore, we have set a density at 15 ° C. at 820-880 Kg / M3 or less and are precursors with hydrocarbons derived from a combination of light tight oil and hydroconverted high sulfur fuel oil. Alternatively, they have found that by utilizing the production of components, fuels with a very low sulfur content of 0.1% by weight can be blended or produced. The fuel has an initial boiling point, which is the lowest boiling point of any distillate of the oil under atmospheric distillation conditions, and a highest boiling point, which is the highest boiling point of the residual portion of the high sulfur fuel oil, which is soluble in a solvent suitable for solvent separation. Has a boiling point. For example, when practicing the present invention, if heptane is used as a solvent for acquisition metrics for obtaining combined components, or as a solvent for manufacturing using the solvent separator in the manufacturing process of the present invention. The highest boiling point in the combination, whether treated or untreated, is higher than when pentane is selected as the metric or solvent for production.

We have selected (L) + (M) + (H) precursors to envision a wide range of hydrocarbon blended fuel combinations useful as clean turbine fuels in the methods of the present disclosure described above. We found that it could be used for processing. The turbine fuel has the following characteristics. (A) 0.05 wt% (500 ppm) to 0.1 wt% (1000 ppm) sulfur according to ISO8754, (b) density of 820-880 kg / M3 at 15 ° C. according to ASTM D4052, ( c) Total metals of 25 ppm or less, preferably less than 10 ppm by weight, more preferably less than 1 ppm by weight, according to ISO 14597, (d) 43.81-45.15 MJ / kg HHV, and (e) 41. LHV from 06 to 42.33 MJ / kg. The flash point varies based on the lowest flash point component of the combination. We have found variants with the following additional expected properties: (A) The kinematic viscosity at 50 ° C. below 10 mm ² / s (1 mm ² / s = 1 cSt in ISO 3104), (b) the carbon residue according to ISO 10370 is 0.32-1.5, and ( c) The actual gum according to ISO 6246 is less than 5, (d) the oxidation stability according to ASTM D2272 is about 0.5, and (e) the acid value according to ASTM D664 is 0.05 mgKOH / g. For use as a marine fuel, refer to the test or calculation method specified in ISO 2817-10.

Therefore, the present invention is widely applicable to the production of fuels with reduced sulfur and other pollutants and low levels, and the use of such fuels. Certain features may be modified without departing from the spirit or scope of the invention. Therefore, the present invention is not limited to the above-mentioned specific embodiment or embodiment, but is defined only in the appended claims or equivalents.

Claims (12)

Light tight oil combined with treated soluble deasphalt oil and other residues treated by hydroconversion reaction effluent or residue hydrotreatment with lighter material derived from high sulfur fuel oil, treatment liquid and A fuel obtained by forming a effluent with unconverted oil, said unconverted oil passes through solvent separation to remove insoluble residual metals and asphaltene to form soluble deasphalted oil and form. The soluble deasphalted oil produced is subsequently processed by an additional hydrotreatment or additional hydroconversion to form the treated soluble deasphalized oil, the fuel having an actual sulfur content of 0.5. The treatment soluble desorption of less than or equal to the weight, where the initial distillate is the initial distillate of the lowest boiling component of the lighter material from the light tight oil or the combined hydrotransformation, and the highest boiling point is derived from the high sulfur fuel oil. A fuel characterized by having the highest boiling point of the highest boiling point component of an asphaltated oil or other residue in combination. A compounding combination that is useful as a fuel, and the above fuel
The combination obtained by combining a series of hydrocarbon components consisting of (L) + (M) + (H) is (a) (L)% + (M)% + (H) based on a total of 100% by volume. )% = 100%,
If (b) (L)% = (H)% = (100%-(M)%) / 2) and (c) (M)% are zero (zero) or less than 100%, the rest , (L)% / (H)% ratio is determined to be 0.4 / 1 to 0.6 / 1 and formed.
(D) If (M)% of the combination is zero (zero) or less than 100%, the rest have a (L)% / (H)% ratio of 0.4 / 1-0.6 /. Except when the sulfur content is 1 and the sulfur content is 0.25 wt% or less, the final density is (1) within 820 to 880 kg / M3 at 15 ° C., and (2) the sulfur content is 0.5 wt% or less. Amount and (3) have a metal content of 40 ppm by weight or less,
(E) (L) contains components of naphtha and kerosene range material, refined or partially purified, without fractional distillation, hydrothermalization or other treatment steps, except for any separation of light gas or water. Unpurified or extracted and used, has an initial fractionation point of 38 ° C. (100 ° C.) or less, 90% plus end point of 190 ° C. (374 ° C.) to about 205 ° C. (401 ° C.), (L) The range component gives the (L) range bulk density and final combination density even if the individual components of (L) are outside the combination density range.
(F) (M) is a 90% plus of the initial distillation point of about 190 ° C. (374 degrees Fahrenheit) to about 205 ° C. (401 degrees Fahrenheit) and about 385 ° C. (725 degrees Fahrenheit) to 410 ° C. (770 degrees Fahrenheit). Having a refined or partially refined petroleum distillate with an endpoint, the (M) range component is the (M) range bulk density and final, even if the individual components of (M) are outside the combined density range. Give the combination density,
(G) (H) is refined or partially refined petroleum having an initial distillation point of about 385 ° C. (725 ° F.) to about 410 ° C. (770 ° C.) and an end point of about 815 ° C. (1499 ° F.) or less. The end point of (H), which has a distillate, is treated by solvent separation to reduce the presence of asphaltene and metal, then recovered, and then treated by hydrogenation conversion or hydrogenation treatment to make the final sulfur of the combined fuel. It is the highest boiling point of the stream components that have been leveled to be able to be added to the combination of (L), (M) and (H) to satisfy the content, and the (H) range components are the individual constituents of (H). A compounding combination characterized in that it provides the (H) range bulk density and final combination density even if the element is outside the combination density range. The fuel according to claim 2, wherein (M) is present in an amount of 10% to 90%, and the remaining (L) / (H) ratio is 0.4 / 1 to 0.6 / 1. The fuel according to claim 2, wherein (M) is present in an amount of 20% to 80%, and the remaining (L) / (H) ratio is 0.4 / 1 to 0.6 / 1. The fuel according to claim 2, wherein (M) is present in an amount of 30% to 70%, and the remaining (L) / (H) ratio is 0.4 / 1 to 0.6 / 1. The fuel according to claim 2, wherein the sulfur content is 0.1% by weight or less and the metal content is 25% by weight or less. A compounding combination useful as a fuel, the fuel is formed by combining a series of hydrocarbons consisting of (L) + (M) + (H), and the resulting combination has the (M) range component. The (L) / (H) ratio of the remaining portion, which is 30% to 70% by volume and is equal to the parts (L) and (H), is 0.9 / 1-1 / 0, based on a total of 100% by volume. 9, the final combination density is 820-880 kg / M3 at 15 ° C., the total sulfur content is 0.25 wt% or less, the metal content is 40 ppm by weight or less.
(A) (L) contains components of naphtha and kerosene range material, refined or partially purified, without fractional distillation, hydrothermalization or other treatment steps, except for any separation of light gas or water. Unpurified or extracted and used, has an initial fractionation point of 38 ° C. (100 ° C.) or less, 90% plus end point of 190 ° C. (374 ° C.) to about 205 ° C. (401 ° C.), (L) The range component gives the (L) range bulk density and final combination density even if the individual components of (L) are outside the combination density range.
(B) (M) is 90% plus the initial point of about 190 ° C (374 degrees Fahrenheit) to about 205 ° C (401 degrees Fahrenheit) and about 385 ° C (725 degrees Fahrenheit) to 410 ° C (770 degrees Fahrenheit). Having a refined or partially refined petroleum distillate with an endpoint, the (M) range component is the (M) range bulk density and final, even if the individual components of (M) are outside the combined density range. Give the combination density,
(C) (H) is refined or partially refined petroleum having an initial distillation point of about 385 ° C. (725 ° C.) to about 410 ° C. (770 ° C.) and an end point of about 815 ° C. (1499 ° C.) or less. The end point of (H), which has a distillate, is treated by solvent separation to reduce the presence of asphaltene and metals, then recovered, and then treated by hydrogenation conversion or hydrogenation treatment to make the final sulfur of the combined fuel. The highest boiling point of the stream component at a level that can be added to the combination of (L), (M) and (H) to satisfy the content, and the (H) range component is the individual component of (H). Is a compounding combination that gives the (H) range bulk density and the final combination density even if is outside the combination density range. The fuel according to claim 7, wherein the range of (M) is 40% by volume to 60% by volume, and the rest is substantially equal to the portions (L) and (H). The total sulfur content is 0.1% by weight or less, the metal content is 25% by weight or less, and the fuel has hydrocarbons derived from a combination of light tight oil and hydroconverted high sulfur fuel oil. , The fuel is the lowest boiling point of any distillate of any of the oils under atmospheric distillation conditions and the highest of the residual portion of the high sulfur fuel oil soluble in a solvent suitable for solvent separation. The fuel according to claim 7, which has a maximum boiling point, which is a boiling point. A compounding combination useful as a fuel, the fuel is obtained by combining a series of hydrocarbons consisting of (L) + (M) + (H), and the final combination obtained has the following characteristics:
(A) 0.05% by weight (500% by weight ppm) to 0.25% by weight (2500% by weight) sulfur,
(B) Final combination density of 820-880 kg / M3 at 15 ° C.
(C) All metals of 25 ppm by weight or less,
It has (d) 43.81 to 45.15 MJ / kg HHV and (e) 41.06 to 42.33 MJ / kg LHV.
(F) (L) contains components of naphtha and kerosene range material, refined or partially purified, without fractional distillation, hydrothermalization or other treatment steps, except for any separation of light gas or water. Unpurified or extracted and used, has an initial fractionation point of 38 ° C. (100 ° C.) or less, 90% plus end point of 190 ° C. (374 ° C.) to about 205 ° C. (401 ° C.), (L) The range component gives the (L) range bulk density and final combination density even if the individual components of (L) are outside the combination density range.
(G) (M) is 90% plus the initial retention point of about 190 ° C (374 degrees Fahrenheit) to about 205 ° C (401 degrees Fahrenheit) and about 385 ° C (725 degrees Fahrenheit) to 410 ° C (770 degrees Fahrenheit). Having a refined or partially refined petroleum distillate with an endpoint, the (M) range component is the (M) range bulk density and final, even if the individual components of (M) are outside the combined density range. Give the combination density,
(H) (H) is refined or partially refined petroleum having an initial distillation point of about 385 ° C. (725 ° F.) to about 410 ° C. (770 ° C.) and an end point of about 815 ° C. (1499 ° F.) or less. The end point of (H), which has a distillate, is treated by solvent separation to reduce the presence of asphaltene and metal, then recovered, and then treated by hydrogenation conversion or hydrogenation treatment to make the final sulfur of the combined fuel. It is the highest boiling point of the stream components that have been leveled to be able to be added to the combination of (L), (M) and (H) to satisfy the content, and the (H) range components are the individual constituents of (H). A compounding combination characterized in that it provides the (H) range bulk density and final combination density even if the element is outside the combination density range. (A) Kinematic viscosity at 50 ° C. less than 10 mm ² / s (1 mm ² / s = 1 cSt),
(B) Residual carbon content in the range of 0.32-1.5,
(C) Real gum less than 5,
(D) Oxidative stability of about 0.5,
(E) Acid value less than 0.05 mg KOH / g, and (f) 0.05 wt% (500 wt ppm) to 0.1 wt% (1000 wt ppm) sulfur.
The fuel according to claim 10, which has one or more of the above. In a compound fuel having a hydrocarbon conversion reaction effluent that boils below the highest boiling point of the light tight oil and the treated soluble deasphalt oil derived from the high sulfur fuel oil or other residues treated by the hydrocarbon conversion. The fuel is the treatment soluble where the initial distillate is the initial distillate of the lowest boiling component of the lighter material from the light tight oil or the combined hydrocarbon conversion and the highest boiling point is derived from the high sulfur fuel oil. It has a series of hydrocarbons that are the highest boiling point of the highest boiling point component of the deasphaltized oil or other residue combined, and the fuel has a density of within 820-880Kg / M3 at 15 ° C., 0.5% by weight or less. A fuel characterized by having sulfur and a metal of 25 wt ppm or less.

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