WO2016111961A2 - Procédé d'évaluation relative pour flux de naphta - Google Patents

Procédé d'évaluation relative pour flux de naphta Download PDF

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Publication number
WO2016111961A2
WO2016111961A2 PCT/US2016/012113 US2016012113W WO2016111961A2 WO 2016111961 A2 WO2016111961 A2 WO 2016111961A2 US 2016012113 W US2016012113 W US 2016012113W WO 2016111961 A2 WO2016111961 A2 WO 2016111961A2
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WO
WIPO (PCT)
Prior art keywords
gasoline
yield
butane
propane
ethane
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Ceased
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PCT/US2016/012113
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WO2016111961A3 (fr
Inventor
Omer Refa Koseoglu
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2823—Raw oil, drilling fluid or polyphasic mixtures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons

Definitions

  • This invention relates to a method and process for the evaluation of samples of crude oil and its fractions by PIONA gas chromatography analysis.
  • Crude oils are very complex mixtures of many thousands of different hydrocarbons. Depending on the source, the oils contain various proportions of straight and branched-chain paraffins, cycloparaffins, and naphthenic, aromatic and polynuclear aromatic hydrocarbons. The nature of the crude oil governs, to a certain extent, the nature of the products that can be manufactured from it and their suitability for specific applications.
  • the first factor is purely market-dependent and cannot be predicted from the crude oil quality. Accordingly, the crude oil value is determined by the regional crude market and differentials such as freight, quality adjustments, refining cost and competitive pricing.
  • crude oil is first distilled under atmospheric pressure. Gases will rise to the top of the distillation column, followed by lower boiling liquids, including, naphtha, kerosene and diesel oil. Naphtha is not a final product, but is subjected to additional treatment steps, such as hydrotreating and catalytic reforming to produce reformate. The reformate is then sent to a gasoline pool for blending.
  • This method correlates actual crude value with bulk properties. API gravity and sulfur content are widely used for the correlation, and other bulk properties, such as viscosity and pour point, can also be used. This method is relatively simple in terms of the amount of testing required. However, this method may not be reliable when a large range of crudes are being valued. For example, some of the naphthenic crudes may be valued relatively higher, using this method, but this result may not reflect the actual market value for the crude oil.
  • Refining- Value Method Crude oils are evaluated and valued using the refinery yields and process operating costs for each crude stream, typically using a linear program (LP) or other model. Refinery models require detailed physical property information and distillation cuts as determined by a detailed crude oil assay. Process yields and operating costs are used with appropriate product values to calculate refining-value differentials between the crude oils.
  • the refining-value method simulates the process used by refiners for selecting crude oils. Detailed crude oil quality information and the need to run a refinery model for a given refinery to generate the yields make this method more complex than the bulk-property method. If input stream quality changes significantly, a new set of yields must be generated. In relatively simple systems involving only a few crudes with reasonably stable quality, the refining-value method normally provides the most accurate value allocation for a refiner.
  • Distillation- Yield Method This is a simplified version of the refming-value method, which instead of using a linear program or other model will only use the yield of each fraction.
  • These product yields from distilling each crude are used with product values to calculate the relative value of each crude.
  • some physical properties of the distillation cuts are used in the value-adjustment system.
  • the quality information from each crude is relatively simple and includes distillation yields and distillation cut properties.
  • the distillation yield- method is more complex than the bulk-property method, but less complex than the refming-value method. Because it uses product values in the calculation, reliability of crude oil value data is not an issue.
  • the products being valued, however, such as naphtha are not finished products meeting defined specifications. So there is some uncertainty regarding the value adjustment for key properties of the distillation cuts.
  • octane number is the measure of a fuel's ability to prevent detonation in a spark-ignition engine. Measured in a standard single-cylinder, variable-compression-ratio engine by comparison with primary reference fuels, American Standard Testing Material Tests ASTM D-2699 and ASTM D-2700 describe the determination of research and motor octane numbers, respectively. Under mild conditions, the engine measures research octane number (RON), while under sever conditions the engine measures motor octane number (MON).
  • the antiknock index is used. This is the arithmetic average of RON and MON, namely, (R+M)/2. It approximates the road octane number, which is a measure of how an "average" car responds to fuel. It is the most critical property for naphtha/gasoline streams.
  • the RON of a spark-ignition engine fuel is determined using a standard test engine and operating conditions to compare its knock characteristic, defined as knock intensity (KI) with those of primary reference fuel (PRF) blends (containing iso-octane and normal heptane) of known octane number.
  • KI knock intensity
  • PRF primary reference fuel
  • a standard KI guide table relates engine CR to octane number level for this specific method.
  • the fuel-air ratio for the sample fuel and each of the primary reference fuel blends is adjusted to maximize KI for each fuel. While gasoline will have an RON of 85 or higher, naphtha will have an RON below 60.
  • the MON of a spark-ignition engine fuel is determined using a standard test engine and operating conditions to compare its knock characteristic with those of PRF blends of known octane number.
  • CR and fuel-air ratios are adjusted to produce standard KI for the sample fuel, as measured by a specific electronic detonation meter instrument system.
  • a standard KI guide table relates engine CR to octane number level for this specific method.
  • the fuel-air ratio for the sample fuel and each of the PRF blends is adjusted to maximize KI for each fuel.
  • Systems and methods for assigning a value to a naphtha stream are provided.
  • the stream is reformed to a target research octane number, and plural light component fractions and a reformate fraction are obtained; the reformate fraction is analyzed to obtain data indicative of the content naphthenes and aromatics, and in certain embodiments additionally paraffins and iso- paraffins, and in further embodiments additionally paraffins, iso-paraffins olefins, and iso- olefins.
  • the indicative data is used to assign a feed quality.
  • the assigned feed quality is used to assign a total liquid yield and raw products yields, which are individually assigned values.
  • a total naphtha valuation can thus be assigned based on the indicative data.
  • the system and method of the invention can be utilized to valuate naphtha fractions derived from crude oils, which fractions have nominal boiling points in the range of -11.5 to 235°C, and in certain embodiments from 36-180°C.
  • Naphtha fractions vary in composition and, as a result, octane number, which, as discussed above, is a key indicative property for engine- knocking characteristic. The difference in composition and properties make the evaluation of the naphtha fraction difficult.
  • the comparative evaluation method disclosed herein is practiced on straight run naphtha samples.
  • the naphtha fraction is converted to light components and a reformate of a target research octane number in a catalytic reforming process.
  • the reformate is fed into a gas chromatograph to obtain data indicative of the content naphthenes and aromatics, and in certain embodiments additionally paraffins and iso-paraffins, and in further embodiments additionally paraffins, iso-paraffms olefins, and iso-olefins, e.g., known as a PIONA analysis.
  • An algorithm is applied to the total percentages of the naphthenes and aromatics in order to determine a value of the naphtha stream. The value of each of the components is assigned based upon independently determined values at a given time and place that is predetermined by the user.
  • an object of the method and system herein is to facilitate comparison of two or more streams in order to ascertain which stream has a higher value based upon the current value for its constituent fractions. Such data is useful, for instance, to provide the refiner with a basis for deciding which stream should be processed first.
  • Another object of this invention is to provide a method for evaluation of particular naphtha streams derived from crude oils from various sources to establish an objective basis for economic comparison based on specific value.
  • regenerator unit In the description herein, the terms “reformer unit”, “reformer ' and “reforming unit” are used interchangeably, and refer to conventional apparatus used in a catalytic reforming process.
  • FIG. 1 schematically illustrates the hydrotreating and reformation of naphtha and the chromato graph analysis of the resultant streams
  • FIG. 2 is a process flow diagram of additional steps carried out to establish a value for naphtha streams using the system and method herein;
  • FIG. 3 is a block diagram of a component of a system for implementing the invention according to one embodiment.
  • a system and method for determining and assigning yields and valuation of a hydrocarbon sample. Reformate component yields of a naptha fraction derived in certain embodiments from crude oil samples are assigned as a function of the PIONA analysis data of a crude oil sample.
  • the correlations also provide information about naphtha component and total yields without fractionation/distillation (crude oil assays) and enables producers, refiners, and marketers to benchmark the oil quality and, as a result, valuate the oils without perfonning the customary extensive and time-consuming crude oil assays.
  • the systems and methods are applicable for evaluation of naphtha streams derived from crude oils, bitumens, heavy oils, shale oils and from refinery process units including hydrotreating, hydroprocessing, fluid catalytic cracking, coking, and visbreaking or coal liquefaction.
  • FIG. 1 shows the hydrotreating and reforming process 100.
  • a naphtha stream 1 10 to be evaluated is fed into a hydrotreater 1 15 to produce a hydrotreated naphtha stream 120, which is passed to a reformer 125.
  • Light component streams hydrogen (“H2") 130, methane (“CI”) 135, ethane (“C2”) 140, propane (“C3”) 145, and butane (“C4") 150, and reformate (“C5+”) 155, are recovered from reformer 125.
  • Operating conditions are such that the reformate is characterized by a target research octane number.
  • the quality of gasoline as measured by the research octane number, will be uniform.
  • the predetermined research octane number selected can be in the range of from 80 to 100 for products coming from the reforming unit, in certain embodiments in the range of from 95 to 100, and in further embodiments in the range of from 95 to 98, which is the gasoline RON specification. It is to be noted that the yield typically declines with an increase in the target octane number.
  • hydrotreater 1 15 operates under conditions and in the presence of one or more catalysts effective to produce a hydrotreated naphtha stream 120 having sulfur levels below 0.5 ppmw and nitrogen levels below 0.5 ppmw.
  • the maximum allowable sulfur and nitrogen contaminant content levels should be maintained within the predetermined limits established for efficient use of the reformer unit catalyst.
  • the reformer catalyst is made of noble metals such as platinum and palladium and is very sensitive to impurities like sulfur and nitrogen. The presence of higher levels of sulfur and nitrogen during the operation will poison the catalyst.
  • the major sources of sulfur are inadequate hydrotreating, hydrotreating stripper upsets and the recombination of hydrogen sulfide and olefins at high temperature and low pressures.
  • the principal sources of nitrogen are inadequate hydrotreating, cracked naphtha in the feedstock, and improper use of inhibitors. Since the reforming unit catalyst can be quite sensitive to impurities, in certain embodiments sulfur and nitrogen levels are reduced in the hydrotreating process to provide a reformer feedstream meeting the requisite specification.
  • the separated light gases 130, 135, 140, 140, 150 are passed into one or more refinery gas analyzers 160, for instance in certain embodiments gas chromatographs that analyze the gases in accordance with ASTM D1945.
  • Liquid reformate 155 is fed into PIONA analyzer 165.
  • PIONA analyzer 165 is a gas chromatograph that analyzes the liquid in accordance with ASTM D6839. In the PIONA analysis, fractions of the reformate are tabulated by carbon number and n- paraffins, i-paraffins, naphthenes and aromatics, showing the percentage volume for each carbon number.
  • the reformate is derived from straight-run naphtha from crude oil distillation, as opposed to being derived from intermediate refinery naphtha from cracking reactions, and accordingly no or few olefins are present.
  • FIG. 2 shows a process flowchart of steps in a method according to one embodiment herein.
  • Variable N is used to represent the total percentage of naphthenes by volume
  • variable A is used to represent the total percentage of aromatics by volume, as derived from the PIONA analysis indicated at step 165 in FIG. 2.
  • step 220 the feed quality is assigned as:
  • step 230 the total liquid yield, Y, is assigned as a function of the feed quality and the constant RON number (i.e., the target number), Rt:
  • the individual yields for H2, C I , C2, C3, C4 and C5+ and the reformate yield can then be assigned.
  • the estimated raw product yields are assigned, for instance using equations (3) - (8), for methane, ethane, propane, butane and gasoline, using linear models based upon the total liquid products variable, while hydrogen is modeled linearly based upon the total liquid products variable and the constant RON number, Rt.
  • the estimated total raw yield is the sum of the estimated raw yields for these
  • step 250 the yields are normalized to 100 by dividing the individual raw yields by the total raw yields, as follows:
  • step 260 the estimated yield of each fraction is multiplied by its unit value, to assign a value to each fraction:
  • NPT Civ + C2v + C3v + C4v + Gv + Hv (22)
  • the value of the naphtha stream can also be restated as $/barrel, by dividing the value expressed as $/ton by the density and multiplying by the number of liters in a barrel of oil (159 liters/barrel):
  • NPB (NPT / Density) * 159 liters/barrel (23)
  • Computer system 300 includes a processor 310, such as a central processing unit, an input/output interface 320 and support circuitry 330.
  • processor 310 such as a central processing unit
  • input/output interface 320 and support circuitry 330.
  • a display 340 and an input device 350 such as a keyboard, mouse or pointer are also provided.
  • the display 340, input device 350, processor 310, input/output interface 320 and support circuitry 330 are shown connected to a bus 360 which also connects to a memory unit 370.
  • Memory 370 includes program storage memory 380 and data storage memory 390.
  • computer 300 is depicted with the direct human interface components of display 340 and input device 350, programming of modules and importation and exportation of data can also be accomplished over the interface 320, for instance, where the computer 300 is connected to a network and the programming and display operations occur on another associated computer, or via a detachable input device, as are well known in the art for interfacing programmable logic controllers.
  • Program storage memory 380 and data storage memory 390 can each comprise volatile (RAM) and non-volatile (ROM) memory units and can also comprise hard disk and backup storage capacity, and both program storage memory 380 and data storage memory 390 can be embodied in a single memory device or separated in plural memory devices.
  • Program storage memory 380 stores software program modules and associated data, including one or more calculation modules such as a feed quality calculation module (e.g., corresponding to step 220 described above with respect to FIG. 2), yield calculation modules (e.g., corresponding to steps 230, 240 and 250 described above with respect to FIG.
  • Data storage memory 390 stores data used and/or generated by the one or more modules of the present system, including PIONA analysis data or portions thereof used by the one or more modules of the present system, and calculated feed quality, yields and valuations generated by the one or more modules of the present system.
  • the computer system 300 can be any general or special purpose computer such as a personal computer, minicomputer, workstation, mainframe, a dedicated controller such as a programmable logic controller, or a combination thereof. While the computer system 300 is shown, for illustration purposes, as a single computer unit, the system can comprise a group/farm of computers which can be scaled depending on the processing load and database size, e.g., the total number of samples that are processed and results maintained on the system. The computer system 300 can serve as a common multi-tasking computer.
  • the computing device 300 preferably supports an operating system, for example, stored in program storage memory 390 and executed by the processor 310 from volatile memory.
  • the operating system contains instructions for interfacing the device 300 to the calculation module(s).
  • the operating system contains instructions for interfacing computer system 300 to the Internet and/or to private networks.
  • equations (1) - (23) can be used to assign the naptha value as a function of the feed quality and the target RON number, Rt.
  • N 14.98
  • A 8.05
  • Equations and constants for assigning total reformer yield were developed from a linear regression of the N+2A concentration versus total yield.
  • the individual yields for H2, CI , C2, C3, C4 and C5+ and the total reformate yield were calculated from a linear regression of the total reformate yield versus individual yields at the target research octane number. For these calculations, the following constants are applied:
  • the individual raw product yields are as follows:
  • the Total Raw Yield is:
  • the present invention can be implemented as a computer program product for use with a computerized computing system.
  • programs defining the functions of the present invention can be written in any appropriate programming language and delivered to a computer in any form, including but not limited to: (a) information permanently stored on non-writeable storage media (e.g., read- only memory devices such as ROMs or CD-ROM disks); (b) information alterably stored on writeable storage media (e.g., floppy disks and hard drives); and/or (c) information conveyed to a computer through communication media, such as a local area network, a telephone network, or a public network such as the Internet.
  • non-writeable storage media e.g., read- only memory devices such as ROMs or CD-ROM disks
  • writeable storage media e.g., floppy disks and hard drives
  • information conveyed to a computer through communication media such as a local area network, a telephone network, or a public network such as the Internet.
  • the system embodiments can incorporate a variety of computer readable media that comprise a computer usable medium having computer readable code means embodied therein.
  • One skilled in the art will recognize that the software associated with the various processes described can be embodied in a wide variety of computer accessible media from which the software is loaded and activated.
  • the present invention contemplates and includes this type of computer readable media within the scope of the invention.
  • the scope of the present claims is limited to computer readable media, wherein the media is both tangible and non-transitory.

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  • Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un système et un procédé permettant de déterminer la valeur relative d'un produit de naphta consistant à reformer le naphta en fractions à un indice d'octane recherche (RON) de constante prédéfinie, à réaliser une analyse PIONA sur le reformat, des modules ou des étapes étant ensuite mises en œuvre pour attribuer la qualité de la charge d'alimentation, attribuer les rendements totaux en liquide, attribuer les rendements en produit brut, normaliser les rendements en produit brut attribués, attribuer une valeur à une ou plusieurs fractions, et calculer une valeur totale du flux de naphta. Le procédé est répété sur des échantillons de différents pétroles bruts afin de fournir des valeurs relatives au RON prédéfini à des fins de comparaison.
PCT/US2016/012113 2015-01-05 2016-01-05 Procédé d'évaluation relative pour flux de naphta Ceased WO2016111961A2 (fr)

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Cited By (2)

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CN111429973A (zh) * 2019-06-19 2020-07-17 浙江中控技术股份有限公司 用于汽油产品中分子信息的实时计算方法
CN111899809A (zh) * 2020-06-12 2020-11-06 中国石油天然气股份有限公司 一种汽油调合配方的优化方法、系统、装置及存储介质

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111429973A (zh) * 2019-06-19 2020-07-17 浙江中控技术股份有限公司 用于汽油产品中分子信息的实时计算方法
CN111429973B (zh) * 2019-06-19 2024-10-25 中控技术股份有限公司 用于汽油产品中分子信息的实时计算方法
CN111899809A (zh) * 2020-06-12 2020-11-06 中国石油天然气股份有限公司 一种汽油调合配方的优化方法、系统、装置及存储介质
CN111899809B (zh) * 2020-06-12 2023-12-29 中国石油天然气股份有限公司 一种汽油调合配方的优化方法、系统、装置及存储介质

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