EP1238043B1 - Procede permettant d'ameliorer le processus de craquage thermique et les rendements des produits resultants - Google Patents

Procede permettant d'ameliorer le processus de craquage thermique et les rendements des produits resultants Download PDF

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EP1238043B1
EP1238043B1 EP00980659A EP00980659A EP1238043B1 EP 1238043 B1 EP1238043 B1 EP 1238043B1 EP 00980659 A EP00980659 A EP 00980659A EP 00980659 A EP00980659 A EP 00980659A EP 1238043 B1 EP1238043 B1 EP 1238043B1
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parameter
thermal cracking
conditions
cracking
heavy hydrocarbons
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EP1238043A1 (fr
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Gregory M. Jones
Michael Brauchle
Uwe Hoffman
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Baker Hughes Holdings LLC
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Baker Hughes Inc
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    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • C10G9/206—Tube furnaces controlling or regulating the tube furnaces

Definitions

  • This invention relates to a method for improved thermal cracking, such as visbreaking, on-purpose coking or delayed coking, of hydrocarbons, particularly heavy hydrocarbons.
  • thermal cracking or conversion process is a process, which, by using thermal energy, i . e . heat and temperature, converts, or cracks larger hydrocarbon molecules, particularly those having boiling points higher than about 350°C, into smaller ones.
  • thermal energy i . e . heat and temperature
  • high boiling, heavy and lower valued residues from an oil refinery or chemical plant may be converted into lower boiling, light or intermediate and higher valued product cuts.
  • thermal cracking reactions include, visbreaking, hydrocracking (cracking reaction in the presence of added hydrogen), and various on-purpose coking or delayed coking processes.
  • thermal cracking operations are prone to severe fouling problems, including coking. Visbreaking is such an example.
  • Visbreaking is a thermal cracking reaction, in which heavy hydrocarbon feedstocks such as resids with high viscosity are fed into a reactor at a temperature high enough to cause these feedstocks to break down into smaller ones.
  • the liquid product stream usually exhibits lower viscosity, or otherwise referred to as being visbroken.
  • This product can be used as fuel oil.
  • visbreaking today has the added importance of obtaining a maximum of conversion of heavy materials into middle and light distillate fractions products such as naphtha and gas oil. Gas oil and naphtha are useful as components for transportation fuel. This trend in the market place is particularly obvious in Europe and most other industrialized countries.
  • the charge (feedstock) is fed to and becomes preheated in a train of heat exchangers.
  • This preheated charge is then sent to a furnace (or cracking unit) for the intended thermal cracking.
  • the furnace is normally one or a plurality of tubes or reactors.
  • the products from cracking pass through a fractionation column to separate the products.
  • the tar from the cracking reaction is separated and removed from the bottom of the fractionation column and sent to one or more heat exchangers to recover some of the heat content, which may be used for preheating the charge.
  • the outlet temperature of a soaker is usually lower than the furnace outlet temperature by about 20 to 30°C.
  • the residence time in a soaker is usually in the range of from about 10 minutes to about 30 minutes.
  • the pressure in a soaker is usually in the range of from about 3 bar (300 kPa) to about 20 bar (2 MPa).
  • the thermal cracking units are normally operated at a temperature in the range of from about 420°C to about 500°C and a pressure in the range of from about 3 bar (300 kPa) to about 20 bar (2 MPa).
  • a temperature in the range of from about 420°C to about 500°C and a pressure in the range of from about 3 bar (300 kPa) to about 20 bar (2 MPa).
  • the operating temperature of the furnace is close to the low end of the temperature range if there is a soaker between the furnace and the fractionation column. A temperature near the high end of the range is preferred if there is no soaker.
  • a thermal cracking unit such as a visbreaking unit, is normally sized for a desired level of conversion of the feedstock at a desired flow rate.
  • conversion is used herein to mean the combined weight % of both the light distillate and the middle distillate, including gaseous products, naphtha and gas oil, relative to the total weight of the charge to the furnace.
  • the products recovered from the fractionation column have the following distribution of components: about 3 wt% to about 10 wt% of light distillates; about 10 wt% to about 20 wt% middle distillates; and about 70 wt% to 85 wt% of tar as heavy residue, which is removed from the bottom of the fractionation column. All of these weights are based on the weight of the feedstock.
  • Typical feedstocks to a visbreaking unit comprise of heavy bottom products from upstream atmospheric or vacuum distillation units or plants.
  • the fouling characteristics of a particular feedstock under the visbreaking conditions are often the most important controlling factors in operating a visbreaking unit. These characteristics tend to dictate the visbreaking temperature, which, in turn and at a particular flow rate, controls the conversion level of the charge and the yields of the desired light fractionations. Because the conversions are usually below 20 wt%, even an increase of just one wt% in conversion may have a significant impact on process economics and profitability.
  • a higher conversion level requires a higher operating temperature in the cracking unit, a longer residence time (i.e. lower flow rate) or both.
  • a proper balance between operating conditions and fouling rates will allow longer operating time and produce more desired products before the cracking unit and other parts of the plant have to be shut down for cleanups, maintenance or repairs. Due to the chemistry involved and the nature of the feedstocks, it is generally believed that it is not possible to achieve total elimination of fouling from a thermal cracking reaction of heavy hydrocarbons such as visbreaking.
  • SU 783334 discloses a system using temperature, pressure and residue quality sensors for sensing operating conditions in an oil refining system and for adjusting the fuel intake of this system.
  • the preferred embodiment provides such a method with short response times in measuring two parameters to allow quick adjustments of the reaction conditions for optimizing the conversion-fouling profile of the thermal cracking reaction, particularly a visbreaking reaction.
  • the preferred embodiment also provides a method, which is automated to make adjustments of cracking, including visbreaking, conditions to maximize conversion while keeping fouling within acceptable levels.
  • One object of a preferred embodiment is to provide a method for improved thermal cracking of heavy hydrocarbons, such as visbreaking of vacuum distillation residue (resid), atmospheric distillation residue, crude oil, FCC (fluid catalytic cracking) slurry oil and mixtures thereof.
  • the method comprises cracking the heavy hydrocarbons in a unit under first conditions effective to produce a product, separating the product into a light fraction and a bottoms fraction, measuring a parameter, such as asphaltene colloidal stability and/or amount of coke particles, of the bottoms fraction, making a determination of whether the parameter is outside of a limit, and adjusting the first conditions in response to the determination.
  • a parameter such as asphaltene colloidal stability and/or amount of coke particles
  • the preferred embodiment also relates to a system for conducting improved thermal cracking of heavy hydrocarbons.
  • the system comprises a cracking unit comprising a cracking furnace, including a plurality of furnace tubes to crack the heavy hydrocarbons under first conditions effective to produce a product, a separation unit such as a fractionation column to separate the product into a light fraction and a bottoms fraction, at least one sensor to measure at least one parameter such as asphaltene colloidal stability and/or amount of coke particles, at least one processor to make a determination if the at least one parameter is outside of a limit, and at least one controller to adjust the first conditions in response to the determination.
  • a cracking unit comprising a cracking furnace, including a plurality of furnace tubes to crack the heavy hydrocarbons under first conditions effective to produce a product, a separation unit such as a fractionation column to separate the product into a light fraction and a bottoms fraction, at least one sensor to measure at least one parameter such as asphaltene colloidal stability and/or amount of coke particles, at least
  • Another object of a preferred embodiment relates to a method for and a system of converting the bottoms fraction from a thermal cracking unit such as visbreaker into desired coke products in at least one coker or at least one delayed coker.
  • the preferred embodiment provides a method for and a system of performing an improved thermal cracking, such as visbreaking, of heavy hydrocarbons by (a) monitoring fouling, particularly propensity of precipitation of asphaltenes or aggregation of asphaltene colloids and coking of the bottoms fraction of the cracking product, and (b) adjusting the cracking conditions in response to the data collected during monitoring.
  • the object is to maximize conversions of heavy hydrocarbons and at the same time keeping fouling (such as asphaltene precipitation and/or coking or coke formation) within acceptable and/or predetermined limits.
  • the preferred embodiment also relates to an improved coking process, including thermal coking and delayed coking processes.
  • the bottoms fraction composition is adjusted so that it becomes a better feedstock for a downstream coker(s) or delayed coker(s), which are operated at a realtively high temperature.
  • Two separate parameters corresponding to fouling are independently monitored and measured in the preferred embodiment, particularly for visbreaking of vacuum and/or atmospheric distillation resids type thermal cracking reactions.
  • the data collected from the measurements are compared with predetermined limits to determine if the thermal cracking conditions (a) may be changed or adjusted to achieve a higher conversion or (b) need to be modified to reduce fouling.
  • the predetermined limits may be set by past experience or data collected in the same, similar or related operations, published results, results from conducting additional laboratory experiments, theoretical calculations, modeling, updates of existing model, and combinations thereof.
  • parameters may be monitored and/or measured to provide the needed data for adjusting the, thermal cracking reaction operating conditions.
  • parameters include, but are not limited to the stability of asphaltene/asphaltene colloids in the bottoms product exiting the cracking units, the viscosity of the bottoms fraction, the pour point of the bottoms fraction, the amount of coke particles in the bottoms the chemical composition of the bottoms fraction, combinations thereof and others.
  • a preferred first parameter measures the precipitation and/or a propensity for such precipitation of asphaltenic compounds, collectively referred to herein as asphaltenes, on the surface of the heat exchangers, the furnace or furnace tubes, the soaker (if there is one in the system), or other parts of the system. ( See Figure 3 )
  • Asphaltenes Most of typical visbreaking feedstocks comprise asphaltenes, paraffinic compounds, aromatic compounds and minor amounts of various other compounds, including heteroatom-containing compounds.
  • Typical asphaltenes are dark brown to black-colored amorphous solids with complex structures, relatively high molecular weight and relatively low hydrogen content.
  • asphaltenes In addition to carbon and hydrogen In the composition, asphaltenes also contain nitrogen, oxygen and sulfur species or compounds.
  • asphaltenes typically have some solubilities and/or exist in stabilized colloidal form in the crude oil, atmospheric distillation resid, vacuum distillation resid, mixtures thereof or in certain organic solvents like carbon disulfide.
  • asphaltenes are essentially insoluble in solvents like light naphthas, which are the major products from thermal cracking reactions like visbreaking. Consequently, asphaltenes have a tendency of precipitating and/or aggregating out of the thermal cracking products and depositing on the surface of the equipment or pipes because the naphtha content in the cracking product Is higher than that originally present in the feedstock charge prior to undergoing thermal cracking or visbreaking or on-purpose coking or delayed coking.
  • a preferred second parameter monitors and measures the degree or severity of dehydrogenations, both thermal and catalytic dehydrogenations, which take place during a thermal cracking reaction such as visbreaking. Severe dehydrogenation reactions lead to highly carbonaceous materials like coke. This coke formation phenomenon is also referred to herein as coking. Coking generally becomes much more severe when the thermal cracking_temperature is above a certain temperature, usually between about 400°C and about 500°C, which depends on the feed and operating conditions and equipment ( See Figure 2 ) It should be mentioned that the number of carbon particles In a feed (charge) itself generally remains fairly constant when coming from a particular source.
  • the data collected in the measurement of the second parameter are related to the number of coke or carbon particles within a unit volume of oil, i.e. the bottoms fraction of the product of the thermal cracking reaction.
  • the measurement usually determines only those particles smaller than about 30 microns ( ⁇ ) in diameter, more often only those smaller than about 20 ⁇ and larger than about 1 ⁇ per milliliter of a diluted bottoms fraction (tar).
  • the data collected from the measurements may be used to monitor, control or adjust operating conditions of the furnace tube and/or the soaker. If present, either independently or together, depending on the feedstock charge, the reaction conditions, the equipment of the system and the desired outcome.
  • the data collected from the measuring and/or analytical instrument are sent to one or more data processing units or processors, which are either on-site, at a remote location or both.
  • the processor(s), such as computers can compare the data with a limit or set of limits to determine whether the collected data are outside of the limits.
  • the determinations are used to adjust, if needed, the thermal cracking reaction operating conditions, including, but not limited to thermal cracking temperature, furnace outlet temperature (also referred to herein as reactor outlet temperature interchangeably), pressure, residence time, flow rate of the heavy hydrocarbons, injection of additives and combinations thereof. Operating conditions related to a soaker, if there is one used in the system, may be adjusted in accordance with the determinations as well.
  • These operating conditions of a soaker include, but are not limited to, residence time of the product in the soaker, if and what gas or gas mixtures to be injected into the soaker, the flow rate(s) of the gas(es), the temperature(s) of the gas(es), the quantity of the gas(es) and combinations thereof. ( infra )
  • the processors or computers are capable of issuing commands to the controllers of the various operating conditions in accordance with one or more models. It is within the embodiment of the present invention to use the data collected to modify, refine or refresh the set of reference data and/or the models continuously, intermittently, at a preset interval, upon a triggering point or event or a combination thereof.
  • the one or more models may be updated or modified online or off-line, continuously or periodically. It is also possible to house one or more of the processors with one or more of the analytical instrument or one or more of the various controllers.
  • Various processors and/or computers may be on-site, at a remote location or both.
  • the collected data may be used directly to adjust all of the operating conditions mentioned herein and particularly those in the preceding paragraph, if needed.
  • the models may be modified either online or off-line, continuously or periodically.
  • the first parameter measures and monitors the precipitation of asphaltenes and/or the stability asphaltene colloids, i.e. propensity for forming precipitates in a particular mixture. All of these different asphaltene precipitation mechanisms are usually difficult and time-consuming to be quantified individually. Accordingly, they are collectively referred to herein as asphaltene colloidal stability. There are several ways of carrying out this measurement to determine asphaltene colloidal stability. Examples include flocculation ratio method (FR), peptisation index (PV, i.e. peptisation value) and other methods such as the so-called Martin Bailey method (MB), hot filtration test (HFT), Shell hot filtration test, ASTM D-1661, ASTM D-4870 and UOP 1174 methods.
  • FR flocculation ratio method
  • PV peptisation index
  • MB so-called Martin Bailey method
  • HFT hot filtration test
  • Shell hot filtration test ASTM D-1661, ASTM D-4870 and UOP 1174 methods.
  • ISI infrared stability index
  • NIR near infrared
  • a first volume amount of a sample, such as a heavy tar residue from a visbreaking reactor (furnace) is obtained.
  • This sample is then diluted with a fixed volume amount of a suitable aromatic solvent, such as benzene, toluene, xylenes, C 9 to C 10 aromatics and mixtures thereof to form a mixture.
  • a suitable aromatic solvent such as benzene, toluene, xylenes, C 9 to C 10 aromatics and mixtures thereof to form a mixture.
  • the volume of the aromatic solvent to the volume of the tar residue is in the range of from about 10 to 1 to about 1 to 10, preferably in the range of from about 1 to 1 to about 1 to 5.
  • a paraffinic solvent such as light naphtha, butane, pentane, hexane, heptane, mixtures and others, is then added to this mixture, with the help of the automatic titrator or other suitable equipment, to dose and measure the amount needed to induce flocculation in and the infrared stability index of the mixture.
  • a flocculation point is reached when detectable aggregation occurs in the sample because the paraffinic solvent is actually used as an "anti-solvent.” This point is also the end point of the titration.
  • a heptane such as n-heptane is a preferred paraffinic solvent. While butanes and pentanes may be more sensitive than heptane, their lower boiling points and the corresponding higher vapor pressures make the actual titration operation more difficult.
  • This "infrared stability index" or ISI can be determined by a method such as light absorbance and/or scattering using at least one light source and at least one probe, such as an NIR probe. Infrared (about 25 ⁇ m to about 2.5 ⁇ m) or visible light (about 750 nm to about 400 nm) sources may also be used. NIR means the light has a wavelength in the range of from about 2.5 ⁇ m to about 750 nm. NIR, near-infrared, method is preferred for measuring absorbance or light scattering of dark colored mixtures or solutions, In the probe, the absorbance and/or scattering at one or more wavelengths may be monitored at the same time.
  • the ratio of the volume of the paraffinic solvent to the first volume of the sample is defined as the "first parameter" for purposed of the preferred embodiment. If this first parameter, measured by ISI in the examples below, decreases below a certain value, it is an indication that the asphaltenes and/or asphaltene colloids are becoming too unstable and any precipitation and/or aggregation will become unacceptable to the thermal cracking or visbreaking reaction operator.
  • the severity of the cracking unit needs to be moderated. Cracking conditions such as cracking temperature, furnace outlet temperature and/or residence times may be lowered. Conversely, if the first parameter is much higher than the value, the severity of the cracking unit may be increased to increase conversion of the feed. Depending on the unit, the feed and other operating conditions, this value or limit may vary. In the examples below ( infra ), the predetermined limit is set at about 1.75, preferably about 1.70.
  • the data of the first parameter may be used directly or it can be recorded and stored in a processor to be further analyzed, compared and used to issue commands to alter, adjust or modify one or more thermal cracking (including visbreaking) operating conditions, including those conditions related to the soaker operation, if one is used in the system.
  • the first parameter may also be used in concert with the second parameter ( infra ) to determine any changes or adjustments of one or more of the operating conditions.
  • the infrared stability index is determined in the following manner. As the transparent paraffinic solvent is added to the mixture containing the tar residue and the aromatic solvent, optical absorbance decreases and the incident light transmitted increases. This increase continues until a point where the asphaltenes and/or asphaltene colloids begin to precipitate and/or form aggregates out of the entire mixture. This is the flocculation point determined by the end point of measuring infrared stability index. This precipitation or aggregation is a result of the fact, as discussed earlier, that asphaltenes and/or the asphaltene colloids are practically insoluble in paraffinic solvents. The scattering and/or absorbance of light would cause the transmitted light intensity to decrease again. The decrease will continue as more paraffinic solvent is added because more asphaltenes will precipitate out of the system.
  • the number of carbon or coke particles is determined.
  • the tar residue Prior to the measurement, the tar residue is diluted with a larger amount of aromatic solvent.
  • the total volume of the aromatic solvent to the volume of the tar residue is generally in the range of from about 1,000,000 to 1 to about 1 to 1, preferably from about 100,000 to 1 to about 5 to 1.
  • the number of coke particles is measured.
  • the number of coke particles smaller than about 20 microns and larger than about 1 micron per unit volume of the residue is defined as the second parameter for the feed, the thermal cracking unit and operating conditions of the examples. Similar to ISI, this particle size limit may vary from unit to unit, reaction to reaction and/or feed to feed, depending on the charge (feed), the operating conditions, the operating experience, data collected, baseline information, the particle analyzer used and many other parameters or combinations.
  • the particle-count measurements can be accomplished by using various particle size analyzers.
  • One example is a light-scattering particle size analyzer equipped with a He-Ne (helium-neon) laser light source and the associated electronics.
  • This second parameter or the corresponding data collected can be used directly or it can be recorded and stored in a processor (such as a computer) to be further analyzed, compared and used to issue commands to alter, adjust or modify one or more thermal cracking (including visbreaking) operating conditions, including those conditions related to the soaker operation, if one is used in the system.
  • This second parameter may also be used in concert with the first parameter ( supra ) to determine any changes or adjustments of one or more of the operating conditions.
  • the number of coke particles carbonaceous materials smaller than about 20 microns per unit volume of the tar residue below a level or reference or limit. If the number of the second parameter is much below this limit, it is possible to raise these parameters to increase conversion of the charge. If the parameter is much higher than the limit, it may be necessary to adjust the operating conditions as described in the preceding paragraph, including lowering cracking temperature, lowering FOT and/or decreasing residence time. Too much coke formation indicates that excessive dehydrogenation is occurring in the cracking reaction and this is not desirable. From experience, there also may be coke particles greater than about 20 microns in size. The number is generally low and it is usually difficult to correlate the number with thermal cracking reaction performance of a particular cracking unit.
  • the measured and collected data are normally stored in the analytical instrument and/or separate on-site or remote processors or computers.
  • the data are then compared with the respective references with one or more computer models in order to determine whether any of the operating conditions need to be changes. If changes or adjustments of the operating conditions are needed in accordance with the differences and/or models analyzing the data, proper command signals are sent to various controllers, which in turn change the conditions, such as temperature, flow rate, pressure, gas injection rate in a soaker and others as disclosed herein.
  • One way is to pre-select acceptable limits from past operating experience. Another way may employ theoretical, empirical or semi-empirical methods to calculate the references. It is also possible to use a continuous update method by incorporating the data collected. Certainly, one can use a combination of these different methods in setting the reference points for the first parameter and the second parameter.
  • One or more (computer) models may be used. These models may be related to setting up the reference points, comparison of the collected data with the reference points, issuing commands to controllers in the system in response to the results of the comparisons, and combinations thereof. It is possible to use different processors or computers for different aspects, provided that there is the communication among the processors, analytical instrument, operating condition controllers, and/or other instrument or equipment as needed.
  • references or reference points are determined or selected, if these limits are exceeded (lower in infrared stability index or higher in coke particle count), operating conditions are changed to bring the parameters back to within acceptable ranges. If the data fall far short of the limit(s), the reaction is then not producing high enough conversions. The operating conditions are then changed to increase the conversion of heavy hydrocarbon charge (feedstock) while maintaining the one or, preferably, both parameters within the limits.
  • Figure 1 shows such an integrated system.
  • the system according to Figure 1 operates as follows:
  • Control box 30 generates an electrical signal, which is transmitted to a near-infrared (NIR) probe 10 .
  • NIR probe 10 transduces the electrical signal into an optical signal, which is transmitted into the oil (e.g. a sample of a tar residue from a visbreaker dissolved in an aromatic solvent).
  • the same probe, or optionally a separate sensor 20 detects and measures the changes in intensity of the optical signal at a fixed path length. If there is increasing in the number of asphaltene particles per unit volume of the oil phase, the intensity decreases.
  • Control box 30 amplifies and transmits the detected signal to automated titrator 40 , which doses a clear and transparent paraffinic solvent to the "oil" in a volume that is inversely proportional to the change in signal voltage.
  • the data related to the volume added by titrator 40 is sent to processor or computer 50 .
  • the paraffinic solvent is added to the oil, the optical resistance of the oil decreases.
  • the NIR light incident upon the detector increases.
  • the addition or dosing continues until a infrared stability index is reached, i.e. the asphaltenes or asphaltenic components begin to precipitate out of the oil phase. At his infrared stability index, the optical resistance starts to increase and the detector will detect decreasing light.
  • optical resistance as detected by the detector are transmitted to processor or computer 50 .
  • the data are stored and analyzed. Furthermore, the data are plotted against the volume of the paraffinic solvent added by automated titrator 40 .
  • the infrared stability index is determined and the ratio of the volume of the paraffinic solvent to the volume of oil at the infrared stability index is determined. This is the data for the first parameter.
  • This collected data may be used alone or in combination with the data collected for the second parameter to adjust or change the thermal cracking reaction operating conditions and/or the operating conditions of the soaker, if one such unit is used.
  • particle analyzer 60 is used to determine the number of coke particles per unit volume of oil in the oil sample wherein the particles are smaller than a predetermined size. This size limit is usually between about 1 micron and 20 microns.
  • Coke or carbonaceous materials are not soluble in the organic solvent used to dilute the tar residue.
  • Typical organic solvents include benzene, toluene, the xylenes, C 9 or C 10 aromatics such as pseudocumene and mixtures thereof. It is known that the number of aromatic solvent insoluble particles increases after the thermal cracking reaction. In other words, a thermal cracking reaction such as a visbreaking reaction generates such coke particles.
  • the amount of coke particles in the tar residue has been known to correlate with the amount of coking taking place inside the cracking furnace or furnace tubes.
  • the number of particles measured in this manner is the collected data for the second parameter.
  • This collected data may be used alone or in combination with the data collected for the first parameter to adjust or change the thermal cracking reaction operating conditions and/or the operating conditions of the soaker, if one is used.
  • the furnace outlet temperature is an operating parameter that may be controlled in response to the collected data of the first parameter, the second parameter or both to maximize conversion within acceptable limits of asphaltene precipitation/asphaltene colloid aggregation and coking.
  • the system may be integrated.
  • the various signals, feedbacks and commands may be generated, stored, compared with references or calculated with one or more models by different processors or computers or modules, which may be part of any of the analytical equipment disclosed herein.
  • the entire system can be automated. Alternatively, it may be preferred to automate only part of the system.
  • heavy hydrocarbon as used herein means generally the type of hydrocarbon feedstock or charge or petroleum fluid that contains asphaltene and/or asphaltene colloids and is regularly subjected to thermal cracking or visbreaking in the refining and chemical industries.
  • the structures and compositions of a heavy hydrocarbon are very complex and there could be heteroatom-containing compounds present. Commonly detected heteroatoms include, but are not limited to, oxygen, nitrogen, sulfur and mixtures thereof.
  • Examples of heavy hydrocarbons include vacuum distillation residue (or resid), atmospheric distillation residue, crude oil, FCC slurry oil and mixtures thereof.
  • a soaker is used in the visbreaking system, it is also within the embodiment to use substantially non-reactive gases such as nitrogen, steam or mixtures thereof inside the soaker, particularly in the vicinity of the bottom and the side walls thereof.
  • substantially non-reactive gases such as nitrogen, steam or mixtures thereof
  • the data collected from measuring the two parameters also may be used to adjust the injection of such substantially non-reactive gas or gas mixtures In the soaker. For instance, the quantity, injection rate, injection location, gas temperature and combinations thereof may be adjusted In response to the data. It is preferred to use steam. [see US 5,925,236].
  • the furnace outlet temperature was the operating parameter controlled by the collected data of the first and the second parameters.
  • the example was carried out In a visbreaker unit located In a refinery.
  • a sample of vacuum residue was charged to the unit at a rate in the range of from about 65 to about 95 cubic meters per hour (m 3 /h).
  • Typical furnace outlet temperatures (FOT) were in the range of from about 455°C to about 465°C. Conversions of the feed was about 15.4 wt%. In other words, the light fraction of the product stream Is 15.4 wt% of the charge and the bottoms fraction of the product stream constitutes the balance.
  • the FOT was increased until the first parameter fell to a predetermined value of 1.7, or until the second parameter rose to a predetermined value of 2500.
  • the flow rate was slightly lower at 87.1 m 3 /h.
  • the first parameter was about 1.86 and the second parameter was about 444.
  • the optimization or improvement of the process was performed in several steps during an eleven-hour period. (see TABLE below)
  • the objective was to operate the thermal cracking to achieve as high a conversion as possible while maintaining both the first parameter and the second parameter within acceptable levels, which represent acceptable asphaltene precipitation, particularly before and after cracking, and coking, particularly during cracking, respectively.
  • FOT was about 462.5°C and the flow rate was about 89.4 m 3 /h.
  • the first parameter was about 1.87 and the second parameter, about 408.
  • the conversion remained steady at about 15.4 wt%.
  • control units or processors to compare the data with one or more models to determine If the reactions are optimized. The decision is then transmitted to controls of the visbreaking unit to vary the reaction conditions such as temperature, residence time (flow rate), pressure and combinations thereof.

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Claims (13)

  1. Procédé pour améliorer le craquage thermique d'hydrocarbures lourds comprenant :
    un craquage d'hydrocarbures lourds dans une unité, sous des premières conditions adéquates pour produire un produit comprenant une fraction légère et une fraction de résidu ; et
    une séparation de la fraction légère de la fraction de résidu ;
    caractérisé par :
    une mesure d'un paramètre de la fraction de résidu, dans lequel le paramètre est sélectionné dans le groupe qui comprend la stabilité colloïdale de l'asphaltène, la quantité de particules de coke et une combinaison de celles-ci ;
    un dosage permettant de savoir si le paramètre se trouve ou pas en dehors d'une limite ; et
    le réglage des premières conditions en réponse au dosage.
  2. Procédé selon la revendication 1, dans lequel le craquage thermique est une vis coréduction.
  3. Procédé selon la revendication 2, dans lequel les hydrocarbures lourds sont sélectionnés dans le groupe qui comprend un pétrole brut, un résidu de distillation atmosphérique, un résidu de distillation sous vide, un pétrole avec impuretés en suspension obtenu par craquage catalytique fluide et des mélanges de ceux-ci.
  4. Procédé selon l'une quelconque des revendications 1, 2 ou 3, dans lequel les premières conditions comprennent la température de craquage thermique, la température à la sortie du four, la pression, le temps de séjour et le débit d'écoulement des hydrocarbures lourds.
  5. Procédé selon la revendication 1, dans lequel le craquage thermique est une viscoréduction et l'unité de craquage comprend en outre un maturateur qui fonctionne sous des deuxièmes conditions.
  6. Procédé selon la revendication 1, dans lequel la fraction de résidu est utilisée comme produit de base pour au moins un cokeur ou au moins un cokeur à effet différé.
  7. Procédé selon la revendication 6, comprenant en outre un réglage des deuxièmes conditions en réponse au dosage.
  8. Système de réalisation d'un craquage thermique amélioré d'hydrocarbures lourds, le système comprenant :
    une unité de craquage comprenant un four de craquage pour craquer les hydrocarbures lourds sous des premières conditions adéquates pour produire un produit ; et
    une colonne de fractionnement pour séparer le produit en une fraction légère et une fraction de résidu ;
       caractérisé par au moins un détecteur (10) pour mesurer au moins un paramètre de la fraction de résidu, dans lequel le paramètre est sélectionné dans le groupe qui comprend la stabilité colloïdale de l'asphaltène, la quantité de particules de coke et une combinaison de celles-ci ;
       au moins un processeur (30) pour procéder à un dosage afin de savoir si au moins le ou un des paramètre(s) se trouve en dehors d'une limite ; et
       au moins un contrôleur pour régler les premières conditions en réponse au dosage.
  9. Système selon la revendication 8, dans lequel le craquage thermique est une viscoréduction et les hydrocarbures lourds sont sélectionnés dans le groupe qui comprend un pétrole brut, un résidu de distillation atmosphérique, un résidu de distillation sous vide, un pétrole avec impuretés en suspension obtenu par craquage catalytique fluide et des mélanges de ceux-ci.
  10. Système selon l'une quelconque des revendications 8 ou 9, dans lequel les premières conditions comprennent la température de craquage thermique, la température à la sortie du four, la pression, le temps de séjour et le débit d'écoulement des hydrocarbures lourds.
  11. Système selon la revendication 9, comprenant en outre un maturateur qui fonctionne sous des deuxièmes conditions.
  12. Système selon la revendication 11, dans lequel on injecte dans le maturateur un gaz essentiellement non réactif au voisinage d'une zone sélectionnée parmi son fond, ses parois latérales et des combinaisons de ceux-ci, et dans lequel le gaz est sélectionné parmi l'azote, la vapeur et une combinaison de ceux-ci.
  13. Système selon la revendication 11, dans lequel au moins le ou un des contrôleur(s) pour régler les premières conditions permet en outre de régler les deuxièmes conditions en réponse au dosage.
EP00980659A 1999-11-22 2000-11-21 Procede permettant d'ameliorer le processus de craquage thermique et les rendements des produits resultants Expired - Lifetime EP1238043B1 (fr)

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DK00980659T DK1238043T3 (da) 1999-11-22 2000-11-21 Forbedret termisk krakningsfremgangsmåde og produkter opnået derved

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US44494199A 1999-11-22 1999-11-22
US444941 1999-11-22
PCT/US2000/032061 WO2001038459A1 (fr) 1999-11-22 2000-11-21 Procede permettant d'ameliorer le processus de craquage thermique et les rendements des produits resultants

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US20110278460A1 (en) * 2010-05-13 2011-11-17 Baker Hughes Incorporated Method and apparatus for determining the coke generation tendency of hydrocarbons
US20120298553A1 (en) * 2011-05-27 2012-11-29 Lyondell Chemical Company Predicting petroleum coke morphology from feedstock properties
ITRM20120520A1 (it) 2012-10-30 2014-05-01 Chimec Spa Metodo per il monitoraggio delle condizioni operative in impianti di cracking termico e/o catalitico e relativa apparecchiatura.
US11280779B2 (en) 2017-12-18 2022-03-22 Championx Usa Inc. Solvency for asphaltene deposit remediation or inhibition
IL294130A (en) * 2019-12-24 2022-08-01 Bl Technologies Inc System and method of determining peptization values and visbreaker control

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SU783334A1 (ru) * 1978-07-07 1980-11-30 Куйбышевское Специальное Конструкторское Бюро Московского Научно-Производственного Объединения "Нефтехимавтоматика" Устройство дл автоматического регулировани доли отгона нефтепродукта
US6512156B1 (en) * 1996-10-22 2003-01-28 The Dow Chemical Company Method and apparatus for controlling severity of cracking operations by near infrared analysis in the gas phase using fiber optics

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DE60022674D1 (de) 2005-10-20
WO2001038459A1 (fr) 2001-05-31
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PT1238043E (pt) 2005-11-30
EP1238043A1 (fr) 2002-09-11
ES2245321T3 (es) 2006-01-01
DE60022674T2 (de) 2006-02-02

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