EP4081621A1

EP4081621A1 - System and method of determining peptization values and visbreaker control

Info

Publication number: EP4081621A1
Application number: EP20842614.8A
Authority: EP
Inventors: Steven IMBERT; Conrad Teran; Naveen Agrawal; Rahul JAGTAP; John Hunter; Ruben NACKAERTS; Nimeshkumar PATEL
Original assignee: BL Technologies Inc
Current assignee: BL Technologies Inc
Priority date: 2019-12-24
Filing date: 2020-12-17
Publication date: 2022-11-02
Also published as: WO2021133624A1; IL294130A

Abstract

Disclosed herein are systems and methods of controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and/or tar.

Description

SYSTEM AND METHOD OF DETERMINING PEPTIZATION VALUES AND

VISBREAKER CONTROL

BACKGROUND

[0001 ] The majority of hydrocarbons found on earth naturally occur in crude oil, where decomposed organic matter provides an abundance of carbon and hydrogen which, when bonded, can catenate to form seemingly limitless chains. Hydrocarbons can be refined in a refining process to produce products such as gasoline, diesel fuel, paraffin wax, and the like. The refining process can include a tank-farm, a cold preheat train, a desalter, a hot preheat train, a crude heater/furnace, a crude distillation unit, a vacuum unit furnace, a vacuum distillation unit, and downstream processing units such a hydrotreater, a hydrocracker, fluid catalytic cracking (FCC), a visbreaker, a coker, etc.

[0002] A visbreaker is a non-catalytic processing conversion unit in an oil refinery whose purpose is to reduce the quantity of residual oil produced in the distillation of crude oil and to increase the yield of more valuable light and middle distillates (e.g., gasoil, gasoline, LPG etc.). A visbreaker thermally cracks large hydrocarbon molecules of the atmospheric or vacuum residue in the furnace to reduce its viscosity and to produce valuable distillates. The process name of "visbreaker" refers to the fact that the process reduces (i.e., breaks) the viscosity of the residual oil. As a result the product can meet fuel oil specifications with little or no addition of (valuable) cutter stock.

[0003] Fouling in the visbreaker furnace, soaker, main fractionator, bottom exchangers, piping and other parts of the visbreaker results in throughput or conversion limitations and eventually plant shut down. Often refiners struggle to optimize the conversion of the visbreaker, while maintaining fluid stability (related to asphaltenes) at all locations to avoid fouling. For example, refiners often take a safety margin in conversion due to feed variations (lower furnace output temperature (FOT) when changing the feedstock) and the lack of real-time feedback and accuracy of conventional monitoring techniques on the visbroken tar. Additionally the stability and crackability of the visbreaker feed is rarely monitored at least because the stability measurement (i.e. peptization value) is often time consuming and not accurate (in the high range of the measurement).

[0004] Visbroken tar stability measured by P- value (P_v) is a measure for the state of peptization of asphaltenes in oily media, which measures the maximum allowable dilution of the asphaltene containing oil with aliphatic F1C (heptane/cetane) to bring the asphaltenes on the verge of flocculation. Asphaltenes are dispersed in the continuous phase of visbreaking through the peptizing action of aromatics and resins. Cracking modifies the equilibrium so causing asphaltenes precipitation.

[0005] Definitions of stability terms:

FR = V / (V + V ) arom arom titr l/X = M oil / (V arom + V titr )

P = 1 - FR a max p = FR * ( l + x ) o max min

Pv = P o / (1 - P a ) = 1 + X min

FR = flocculation ratio

FR max = maximum flocculation ratio (at l/X = 0) l X = oil to solution ratio, g/ml

Xm_jn = titrant consumption of undiluted oil, ml/g of oil (at FR = 0)

M Oi ,l = mass of oil, g V arom = volume of aromatic solvent in the mixture, ml v ritr = volume of titrant in the mixture, ml

P_a = peptizability of asphaltenes

P_Q = peptizing power of the oil medium p v = state of peptization of asphaltenes in the oil

[0006] P_v > 1 (typically 1.05 - 1.15).

[0007] Therefore, systems and methods are desired that overcome challenges in the conventional art, some of which are described herein.

SUMMARY

[0008] Disclosed herein are systems and methods of controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar.

[0009] One embodiment of a method of controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar comprises receiving a visbottom sample from a visbreaker, wherein the visbottom sample comprises residual tar from the visbreaker; performing a fingerprint analysis of the visbottom sample to obtain fingerprint spectra; determining a peptization value of the visbottom sample by processing the fingerprint spectra through a generalized predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbottom samples; and operating the visbreaker in accordance with the determined peptization value of the visbottom sample.

[0010] Generally, the visbottom sample is received from the quench circulation of the main fractionator of the visbreaker. [0011] In some aspects of the methods, operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample. Alternatively or optionally, operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample.

[0012] In some aspects of the methods, operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample. In some instances, antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample.

[0013] Alternatively or optionally, the methods may further comprise receiving a visbreaker feed sample, wherein the visbreaker feed sample is obtained prior to a hydrocarbon entering the visbreaker; performing a fingerprint analysis of the visbreaker feed sample to obtain visbreaker feed sample fingerprint spectra; determining a peptization value of the visbreaker feed sample by processing the visbreaker feed sample fingerprint spectra through a generalized feed sample predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbreaker feed samples; and operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed. In some instances, operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed. Alternatively or optionally, operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed. In some instances, operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed. In some instances, the antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

[0014] As noted above, a drawback to conventional visbreaker sampling and analysis is the time it takes to perform the analysis. Using the methods described herein, performing the fingerprint analysis of the visbottom sample and/or performing the fingerprint analysis of the visbreaker feed sample occurs in 10 minutes or less.

[0015] In some aspects of the disclosed methods, the table that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof. In some instances, dilution with automated titration with temperature control comprises a Rofa (ASTM D7060, incorporated by reference), a Porla (ASTM D7157, incorporated by reference) or Zematra (ASTM D7112, incorporated by reference) methods of determining the peptization value. [0016] In some aspects of the disclosed methods, the fingerprint analysis comprises using spectroscopy. In various instances, the spectroscopy comprises one or more of infrared spectroscopy, near-infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

[0017] Further described and disclosed herein are systems and computer-program products for implementing the disclosed methods.

[0018] Additional advantages will be set forth in part in the description which follows or may be learned by practice. The advantages will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive, as claimed.

DRAWINGS

[0019] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments and together with the description, serve to explain the principles of the methods and systems:

FIGS. 1A-1D are simplified overview diagrams of exemplary visbreaker processes, where FIG. 1A illustrates all-coil visbreaking, FIG. IB illustrates soaker visbreaking, FIG. 1C illustrates Shell deep-thermal visbreaking, and FIG. ID illustrates Shell thermal gas-oil visbreaking;

FIG. 2 A illustrates a method according to some embodiments;

FIG. 2B illustrates and exemplary Pv model;

FIG. 3 illustrates an alternate method according to some embodiments; and FIG. 4 is a block diagram of a control system in accordance with some embodiments.

DETAILED DESCRIPTION

[0020] Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or to particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0021] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes-· from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0022] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0023] Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” means “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers or steps. “Exemplary” means “an example of’ and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes.

[0024] Disclosed are components that can be used to perform the disclosed methods and systems. These and other components are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed that while specific reference of each various individual and collective combinations and permutation of these may not be explicitly disclosed, each is specifically contemplated and described herein, for all methods and systems. This applies to all aspects of this application including, but not limited to, steps in disclosed methods. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods.

[0025] The present methods and systems may be understood more readily by reference to the following detailed description of preferred embodiments and the Examples included therein and to the Figures and their previous and following description.

[0026] FIGS. 1A-1D are simplified overview diagrams of exemplary visbreaker processes. FIG. 1A illustrates all-coil visbreaking. FIG. IB illustrates soaker visbreaking. FIG. 1C illustrates Shell deep-thermal visbreaking, and FIG. ID illustrates Shell thermal gas oil visbreaking. These are non-limiting examples of the visbreaking process and the embodiments disclosed herein may be used in visbreaking processes not shown in FIGS. 1A- 1D.

[0027] Though not shown in FIGS. 1A-1D, the visbreaker processes further comprise control systems for controlling and monitoring the process. Generally, the control systems includes processors and sensors for controlling and monitoring the processes. [0028] The disclosed systems and methods enable controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar. In one aspect, as shown in the flowchart of FIG. 2A, this is done by 202 receiving a visbottom sample from a visbreaker. Generally, the visbottom sample comprises residual tar from the visbreaker. Typically, the visbottom sample is received from a quench circulation of the main fractionator of the visbreaker. At 204, a fingerprint analysis is performed of the visbottom sample to obtain fingerprint spectra. Generally, the fingerprint analysis involves spectroscopy. For example, the spectroscopy may comprise one or more of infrared spectroscopy, near-infrared spectroscopy, and nuclear magnetic resonance spectroscopy. Generally, the fingerprint analysis is performed using an analyzer that has an analyzer processor. The fingerprint spectra is the resultant output from a spectrometer device (i.e., analyzer), which quantifies the amount of energy (light) absorbed by matter (in this case by a sample of visbottom). Each wavelength in the resultant spectrum (of wavelength vs absorbance) is measured in nanometers vs absorbance units.

[0029] At 206, results of the fingerprint analysis (i.e., the fingerprint spectra) are provided to a processor. This processor may be the analyzer processor, or more typically is a separate processor. In some instances, the separate processor is part of a control system used to monitor and control the visbreaker. The processor determines a peptization value of the visbottom sample by comparing results of the fingerprint analysis to peptization values. By using advanced mathematical modeling algorithms typical markers from the fingerprint are correlated with peptization values. The fingerprint spectra is processed by the processor using a generalized predictive model. This generalized model has been derived using various computational methods that include correlated component regression and machine learning algorithms. The predictive model has been trained to correlate fingerprint spectral markers (e.g., absorbance units at each of over 1800 wavelengths) vs peptization value for a dataset of visbottom samples. FIG. 2B illustrates such a predictive model 220, where the predictive model 220 is provided fingerprint spectra 222 and outputs a peptization value 224 based on the fingerprint spectra 222. The predictive model 220 has been trained using peptization values for a dataset of samples 226. In some instances, the model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof. For example, dilution with automated titration with temperature control comprises a Rofa (ASTM D7060), a Porla (ASTM D7157) or Zematra (ASTM D7112) method of determining the peptization value

[0030] At 208, the visbreaker is operated in accordance with the determined peptization value of the visbottom sample. This may comprise setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample. Operating the visbreaker in accordance with the determined peptization value of the visbottom sample may also comprise adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample, adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample, and the like. In some instances, antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample.

[0031] FIG. 3 is the process shown and described in FIG. 2 A, with an added steps of 302, receiving a visbreaker feed sample, 304 performing a fingerprint of the visbreaker feed sample to obtain visbreaker feed fingerprint spectra, and 306 determining a peptization value of the visbreaker feed sample by processing the visbreaker feed sample fingerprint spectra through a generalized feed sample predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbreaker feed samples, wherein the generalized feed sample model has been derived using various computational methods that include correlated component regression and machine learning algorithms that has been previously trained to correlate fingerprint spectral markers (absorbance units at each of over 1800 wavelengths) vs peptization value for a dataset of visbreaker feed samples. At step 308, both the peptization value of the visbottom sample and the peptization value of the visbreaker feed sample are used to make operational decisions about the visbreaker. It is to be appreciated that, in some instances, above steps 202-206 and/or 302-306 can be performed in 10 minutes, or less.

[0032] The system has been described above as comprised of units. One skilled in the art will appreciate that this is a functional description and that the respective functions can be performed by software, hardware, or a combination of software and hardware. A unit can be software, hardware, or a combination of software and hardware. The units can comprise software for analysis and controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar. In one exemplary aspect, the units can comprise an analyzer and/or a data analysis computer that comprises one or more computing devices that each comprise a processor 421 as illustrated in FIG. 4 and described below. As used herein, processor refers to a physical hardware device that executes encoded instructions for performing functions on inputs and creating outputs.

[0033] FIG. 4 illustrates an exemplary computer that can be used for executing software for controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar. As used herein, “computer” may include a plurality of computers. The computers may include one or more hardware components such as, for example, a processor 421, a random access memory (RAM) module 422, a read-only memory (ROM) module 423, a storage 424, a database 425, one or more input/output (I/O) devices 426, and an interface 427. Alternatively, and/or additionally, the computer may include one or more software components such as, for example, a computer-readable medium including computer executable instructions for performing a method associated with the exemplary embodiments. It is contemplated that one or more of the hardware components listed above may be implemented using software. For example, storage 424 may include a software partition associated with one or more other hardware components. It is understood that the components listed above are exemplary only and not intended to be limiting.

[0034] Processor 421 may include one or more processors, each configured to execute instructions and process data to perform one or more functions associated with a computer for executing software to perform a method of controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar. Processor 421 may be communicatively coupled to RAM 422, ROM 423, storage 424, database 425, I/O devices 426, and interface 427. Processor 421 may be configured to execute sequences of computer program instructions to perform various processes. The computer program instructions may be loaded into RAM 422 for execution by processor 421.

[0035] RAM 422 and ROM 423 may each include one or more devices for storing information associated with operation of processor 421. For example, ROM 423 may include a memory device configured to access and store information associated with the computer, including information for identifying, initializing, and monitoring the operation of one or more components and subsystems. RAM 422 may include a memory device for storing data associated with one or more operations of processor 421. For example, ROM 423 may load instructions into RAM 422 for execution by processor 421. [0036] Storage 424 may include any type of mass storage device configured to store information that processor 421 may need to perform processes consistent with the disclosed embodiments. For example, storage 424 may include one or more magnetic and/or optical disk devices, such as hard drives, CD-ROMs, DVD-ROMs, or any other type of mass media device.

[0037] Database 425 may include one or more software and/or hardware components that cooperate to store, organize, sort, filter, and/or arrange data used by the computer and/or processor 421. For example, database 425 may store data related to the analysis software. The database may also contain data and instructions associated with computer-executable instructions for performing method of controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar. It is contemplated that database 425 may store additional and/or different information than that listed above.

[0038] I/O devices 426 may include one or more components configured to communicate information with a user associated with computer. For example, I/O devices may include a console with an integrated keyboard and mouse to allow a user to maintain a database of fingerprint/peptization value correlations and determined peptization values, and the like. I/O devices 426 may also include a display including a graphical user interface (GUI) for outputting information on a monitor. I/O devices 426 may also include peripheral devices such as, for example, a printer, a user-accessible disk drive (e.g., a USB port, a floppy, CD-ROM, or DVD-ROM drive, etc.) to allow a user to input data stored on a portable media device, a microphone, a speaker system, or any other suitable type of interface device.

[0039] Interface 427 may include one or more components configured to transmit and receive data via a communication network, such as the Internet, a local area network, a workstation peer-to-peer network, a direct link network, a wireless network, or any other suitable communication platform. For example, interface 427 may include one or more modulators, demodulators, multiplexers, demultiplexers, network communication devices, wireless devices, antennas, modems, and any other type of device configured to enable data communication via a communication network.

[0040] The figures illustrate the architecture, functionality, and operation of possible implementations of systems, methods and computer program products according to various implementations of the present invention. In this regard, each block of a flowchart or block diagrams may represent a module, segment, or portion of code, which comprises one or more executable instructions for implementing the specified logical function(s). It should also be noted that, in some alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based systems that perform the specified functions or acts, or combinations of special purpose hardware and computer instructions.

[0041] The corresponding structures, materials, acts, and equivalents of all means or step plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The implementation was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various implementations with various modifications as are suited to the particular use contemplated.

[0042] Any combination of one or more computer readable medium(s) may be used to implement the systems and methods described hereinabove. The computer readable medium may be a computer readable signal medium or a computer readable storage medium. A computer readable storage medium may be, for example, but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, or device, or any suitable combination of the foregoing. More specific examples (a non-exhaustive list) of the computer readable storage medium would include the following: an electrical connection having one or more wires, a portable computer diskette, a hard disk, a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or Flash memory), an optical fiber, a portable compact disc read-only memory (CD-ROM), an optical storage device, a magnetic storage device, or any suitable combination of the foregoing. In the context of this document, a computer readable storage medium may be any tangible medium that can contain, or store a program for use by or in connection with an instruction execution system, apparatus, or device.

[0043] A computer readable signal medium may include a propagated data signal with computer readable program code embodied therein, for example, in baseband or as part of a carrier wave. Such a propagated signal may take any of a variety of forms, including, but not limited to, electro-magnetic, optical, or any suitable combination thereof. A computer readable signal medium may be any computer readable medium that is not a computer readable storage medium and that can communicate, propagate, or transport a program for use by or in connection with an instruction execution system, apparatus, or device.

[0044] Program code embodied on a computer readable medium may be transmitted using any appropriate medium, including but not limited to wireless, wireline, optical fiber cable, RF, etc., or any suitable combination of the foregoing.

[0045] Computer program code for carrying out operations for aspects of the present invention may be written in any combination of one or more programming languages, including an object oriented programming language such as Java, Smalltalk, C++ or the like and conventional procedural programming languages, such as the "C" programming language or similar programming languages. The program code may execute entirely on the user's computer, partly on the user's computer, as a stand-alone software package, partly on the user's computer and partly on a remote computer or entirely on the remote computer or server. In the latter scenario, the remote computer may be connected to the user's computer through any type of network, including a local area network (LAN) or a wide area network (WAN), or the connection may be made to an external computer (for example, through the Internet using an Internet Service Provider).

[0046] Aspects of the present invention are described herein with reference to flowchart illustrations and/or block diagrams of methods, apparatus (systems) and computer program products according to implementations of the invention. It will be understood that each block of the flowchart illustrations and/or block diagrams, and combinations of blocks in the flowchart illustrations and/or block diagrams, can be implemented by computer program instructions. These computer program instructions may be provided to a processor of a general purpose computer, special purpose computer, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, create means for implementing the functions/acts specified in the flowchart and/or block diagram block or blocks.

[0047] These computer program instructions may also be stored in a computer readable medium that can direct a computer, other programmable data processing apparatus, or other devices to function in a particular manner, such that the instructions stored in the computer readable medium produce an article of manufacture including instructions which implement the function/act specified in the flowchart and/or block diagram block or blocks.

[0048] The computer program instructions may also be loaded onto a computer, other programmable data processing apparatus, or other devices to cause a series of operational steps to be performed on the computer, other programmable apparatus or other devices to produce a computer implemented process such that the instructions which execute on the computer or other programmable apparatus provide processes for implementing the functions/acts specified in the flowchart and/or block diagram block or blocks.

[0049] Although the subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the cl aims.

[0050] Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications, including without limitation those relating to the chemical structures, substituents, derivatives, intermediates, syntheses, compositions, formulations, or methods of use of the invention, may be made without departing from the spirit and scope thereof.

[0051] While the methods and systems have been described in connection with preferred embodiments and specific examples, it is not intended that the scope be limited to the particular embodiments set forth, as the embodiments herein are intended in all respects to be illustrative rather than restrictive.

[0052] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; the number or type of embodiments described in the specification.

[0053] Throughout this application, various publications may be referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the methods and systems pertain.

[0054] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope or spirit. Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit being indicated by the following claims.

Claims

1. A method of controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar, the method comprising: receiving a visbottom sample from a visbreaker, wherein the visbottom sample comprises residual tar from the visbreaker; performing a fingerprint analysis of the visbottom sample to obtain fingerprint spectra; determining a peptization value of the visbottom sample by processing the fingerprint spectra through a generalized predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbottom samples; and operating the visbreaker in accordance with the determined peptization value of the visbottom sample.

2. The method of claim 1, wherein the visbottom sample is received from a quench circulation of a main fractionator of the visbreaker.

3. The method of any one of claims 1 or 2, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample.

4. The method of any one of claims 1-3, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample.

5. The method of any one of claims 1-4, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample.

6. The method of claim 5, wherein antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample.

7. The method of any one of claims 1-6, wherein, the generalized predictive model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof.

8. The method of any one of claims 1-7, further comprising: receiving a visbreaker feed sample, wherein the visbreaker feed sample is obtained prior to a hydrocarbon entering the visbreaker; performing a fingerprint analysis of the visbreaker feed sample to obtain visbreaker feed sample fingerprint spectra; determining a peptization value of the visbreaker feed sample by processing the visbreaker feed sample fingerprint spectra through a generalized feed sample predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbreaker feed samples; and operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

9. The method of claim 8, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises setting a furnace output temperature (FOT) of the visbreaker during tank changes based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

10. The method of any one of claims 8-9, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

11. The method of any one of claims 8-10, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

12. The method of claim 11, wherein antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

13. The method of any one of claims 8-12 wherein performing the fingerprint analysis of the visbottom sample and/or performing the fingerprint analysis of the visbreaker feed sample occurs in 10 minutes or less.

14. The method of any one of claims 1-13, wherein the generalized feed sample predictive model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof.

15. The method of claim 14, wherein dilution with automated temperature-controlled titration comprises a Rofa, a Porla or Zematra method of determining the peptization value.

16. The method of any one of claims 1-15, wherein the fingerprint analysis comprises using spectroscopy.

17. The method of claim 16, wherein the spectroscopy comprises one or more of infrared spectroscopy, near-infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

18. A system for controlling visbreaker fouling and optimizing visbreaker conversion using fingerprinting on visbreaker feed and tar comprising: a memory, wherein the memory stores computer-readable instructions; and a processor communicatively coupled with the memory, wherein the processor executes the computer-readable instructions stored on the memory, the computer-readable instructions causing the processor to: receive a visbottom sample from a visbreaker, wherein the visbottom sample comprises residual tar from the visbreaker; perform a fingerprint analysis of the visbottom sample to obtain fingerprint spectra; determine a peptization value of the visbottom sample by processing the fingerprint spectra through a generalized predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbottom sample; and operate the visbreaker in accordance with the determined peptization value of the visbottom sample.

19. The system of claim 18, wherein the visbottom sample is received from a quench circulation of a main fractionator of the visbreaker.

20. The system of any one of claims 18 or 19, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises the processor setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample.

21. The system of any one of claims 18-20, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises the processor adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample.

22. The system of any one of claims 18-21, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises the processor adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample.

23. The system of claim 22, wherein antifoulant dosages of the visbreaker are adjusted automatically by the processor based on the determined peptization value of the visbottom sample.

24. The system of any one of claims 18-23, wherein, the generalized predictive model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof.

25. The system of any one of claims 18-24, further comprising the processor executing computer-readable instructions stored on the memory that cause the processor to: receiving a visbreaker feed sample, wherein the visbreaker feed sample is obtained prior to a hydrocarbon entering the visbreaker; perform a fingerprint analysis of the visbreaker feed sample to obtain visbreaker feed sample fingerprint spectra; determine a peptization value of the visbreaker feed sample by processing the visbreaker feed sample fingerprint spectra through a generalized feed sample predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbreaker feed samples; and operate the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

26. The system of claim 25, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises the processor setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

27. The system of any one of claims 25-26, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises the processor adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

28. The system of any one of claims 25-27, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises the processor adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

29. The system of claim 28, wherein antifoulant dosages of the visbreaker are adjusted automatically by the processor based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

30. The system of any one of claims 25-29 wherein performing the fingerprint analysis of the visbottom sample and/or performing the fingerprint analysis of the visbreaker feed sample occurs in 10 minutes or less.

31. The system of any one of claims 18-30, wherein the generalized feed sample predictive model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof.

32. The system of claim 31 , wherein dilution with automated temperature-controlled titration comprises a Rofa, a Porla or a Zematra method of determining the peptization value.

33. The system of any one of claims 18-32, wherein the fingerprint analysis comprises using spectroscopy.

34. The system of claim 33, wherein the spectroscopy comprises one or more of infrared spectroscopy, near-infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

35. A non-transitory, computer-readable medium storing instructions that, when executed by a computer processor, cause the computer processor to perform a method useful in a crude oil refinement process, the method comprising: receiving a visbottom sample from a visbreaker, wherein the visbottom sample comprises residual tar from the visbreaker; performing a fingerprint analysis of the visbottom sample to obtain fingerprint spectra; determining a peptization value of the visbottom sample by processing the fingerprint spectra through a generalized predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbottom sample; and operating the visbreaker in accordance with the determined peptization value of the visbottom sample.

36. The computer-readable medium of claim 35, wherein the visbottom sample is received from a quench circulation of 1 fractionator of the visbreaker.

37. The computer-readable medium of any one of claims 35 or 36, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample.

38. The computer-readable medium of any one of claims 35-37, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample.

39. The computer-readable medium of any one of claims 35-38, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample comprises adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample.

40. The computer-readable medium of claim 39, wherein antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample.

41. The computer-readable medium of any one of claims 35-40, wherein, the generalized predictive model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof.

42. The computer-readable medium of any one of claims 35-41, further comprising: receiving a visbreaker feed sample, wherein the visbreaker feed sample is obtained prior to a hydrocarbon entering the main fractionator tank of the visbreaker; performing a fingerprint analysis of the visbreaker feed sample to obtain visbreaker feed sample fingerprint spectra; determining a peptization value of the visbreaker feed sample by processing the visbreaker feed sample fingerprint spectra through a generalized feed sample predictive model that has been trained to correlate fingerprint spectral markers with peptization values for a dataset of visbreaker feed samples; and operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

43. The computer-readable medium of claim 42, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises setting a furnace output temperature (FOT) of the visbreaker during feedstock changes based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

44. The computer-readable medium of any one of claims 42-43, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises adjusting pressures, flows and boiler feed-water (BFW) injections of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

45. The computer-readable medium of any one of claims 42-44, wherein operating the visbreaker in accordance with the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed comprises adjusting antifoulant dosages of the visbreaker based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

46. The computer-readable medium of claim 45, wherein antifoulant dosages of the visbreaker are adjusted automatically based on the determined peptization value of the visbottom sample and/or the determined peptization value of the visbreaker feed.

47. The computer-readable medium of any one of claims 42-46, wherein performing the fingerprint analysis of the visbottom sample and/or performing the fingerprint analysis of the visbreaker feed sample occurs in 10 minutes or less.

48. The computer-readable medium of any one of claims 35-47, wherein the generalized feed sample predictive model that correlates fingerprint results to peptization values is created using peptization values determined using dilution with manual filtrations and visual evaluation, dilution with automated titration, temperature increase with automated titration, or combinations thereof.

49. The computer-readable medium of claim 48, wherein dilution with automated temperature-controlled titration comprises a Rofa, a Porla or Zematra method of determining the peptization value.

50. The computer-readable medium of any one of claims 35-49, wherein the fingerprint analysis comprises using spectroscopy.

51. The computer-readable medium of claim 50, wherein the spectroscopy comprises one or more of infrared spectroscopy, near-infrared spectroscopy, and nuclear magnetic resonance spectroscopy.